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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. 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.

  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.

    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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  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. 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.

  14. 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.

  15. 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.

  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

    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

  9. 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

  10. 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.

  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. 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).

  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)

    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.

  4. 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.

  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

    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

  17. 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.

  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. 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.

  20. 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.

  1. 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.

  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. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  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. 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)

  18. 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.

  19. 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

  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. 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.

  4. 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.

  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.

    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

  13. 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.

  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. 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

  7. 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.

  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. 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.

  7. 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.

  8. 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.

  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. 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

  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. 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

  16. 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

  17. 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

  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

  11. Analysis of a Lipid/Polymer Membrane for Bitterness Sensing with a Preconditioning Process.

    PubMed

    Yatabe, Rui; Noda, Junpei; Tahara, Yusuke; Naito, Yoshinobu; Ikezaki, Hidekazu; Toko, Kiyoshi

    2015-01-01

    It is possible to evaluate the taste of foods or medicines using a taste sensor. The taste sensor converts information on taste into an electrical signal using several lipid/polymer membranes. A lipid/polymer membrane for bitterness sensing can evaluate aftertaste after immersion in monosodium glutamate (MSG), which is called "preconditioning". However, we have not yet analyzed the change in the surface structure of the membrane as a result of preconditioning. Thus, we analyzed the change in the surface by performing contact angle and surface zeta potential measurements, Fourier transform infrared spectroscopy (FTIR), X-ray photon spectroscopy (XPS) and gas cluster ion beam time-of-flight secondary ion mass spectrometry (GCIB-TOF-SIMS). After preconditioning, the concentrations of MSG and tetradodecylammonium bromide (TDAB), contained in the lipid membrane were found to be higher in the surface region than in the bulk region. The effect of preconditioning was revealed by the above analysis methods. PMID:26404301

  12. Nanostructured Membranes from Triblock Polymer Precursors as High Capacity Copper Adsorbents.

    PubMed

    Weidman, Jacob L; Mulvenna, Ryan A; Boudouris, Bryan W; Phillip, William A

    2015-10-13

    Membrane adsorbers are a proposed alternative to packed beds for chromatographic separations. To date, membrane adsorbers have suffered from low binding capacities and/or complex processing methodologies. In this work, a polyisoprene-b-polystyrene-b-poly(N,N-dimethylacrylamide) (PI-PS-PDMA) triblock polymer is cast into an asymmetric membrane that possesses a high density of nanopores (d ∼ 38 nm) at the upper surface of the membrane. Exposing the membrane to a 6 M aqueous hydrochloric acid solution converts the PDMA brushes that line the pore walls to poly(acrylic acid) (PAA) brushes, which are capable of binding metal ions (e.g., copper ions). Using mass transport tests and static binding experiments, the saturation capacity of the PI-PS-PAA membrane was determined to be 4.1 ± 0.3 mmol Cu(2+) g(-1). This experimental value is consistent with the theoretical binding capacity of the membranes, which is based on the initial PDMA content of the triblock polymer precursor and assumes a 1:1 stoichiometry for the binding interaction. The uniformly sized nanoscale pores provide a short diffusion length to the binding sites, resulting in a sharp breakthrough curve. Furthermore, the membrane is selective for copper ions over nickel ions, which permeate through the membrane over 10 times more rapidly than copper during the loading stage. This selectivity is present despite the fact that the sizes of these two ions are nearly identical and speaks to the chemical selectivity of the triblock polymer-based membrane. Furthermore, addition of a pH 1 solution releases the bound copper rapidly, allowing the membrane to be regenerated and reused with a negligible loss in binding capacity. Because of the high binding capacities, facile processing method implemented, and ability to tailor further the polymer brushes lining the pore walls using straightforward coupling reactions, these membrane adsorbers based on block polymer precursors have potential as a separation media that can

  13. Nanoporous thin-film membranes from block-polymers : using self-consistent field theory calculations to guide polymer synthesis.

    SciTech Connect

    Cordaro, Joseph Gabriel

    2010-12-01

    The controlled self-assembly of polymer thin-films into ordered domains has attracted significant academic and industrial interest. Most work has focused on controlling domain size and morphology through modification of the polymer block-lengths, n, and the Flory-Huggins interaction parameter, {chi}. Models, such as Self-Consistent Field Theory (SCFT), have been successful in describing the experimentally observed morphology of phase-separated polymers. We have developed a computational method which uses SCFT calculations as a predictive tool in order to guide our polymer synthesis. Armed with this capability, we have the ability to select {chi} and then search for an ideal value of n such that a desired morphology is the most thermodynamically favorable. This approach enables us to synthesize new block-polymers with the exactly segment lengths that will undergo self-assembly to the desired morphology. As proof-of-principle we have used our model to predict the gyroidal domain for various block lengths using a fixed {chi} value. To validate our computational model, we have synthesized a series of block-copolymers in which only the total molecular length changes. All of these materials have a predicted thermodynamically favorable gyroidal morphology based on the results of our SCFT calculations. Thin-films of these polymers are cast and annealed in order to equilibrate the structure. Final characterization of the polymer thin-film morphology has been performed. The accuracy of our calculations compared to experimental results is discussed. Extension of this predictive ability to tri-block polymer systems and the implications to making functionalizable nanoporous membranes will be discussed.

  14. Nonaffine behavior of three-dimensional semiflexible polymer networks

    NASA Astrophysics Data System (ADS)

    Hatami-Marbini, Hamed

    2016-04-01

    Three-dimensional semiflexible polymer networks are the structural building blocks of various biological and structural materials. Previous studies have primarily used two-dimensional models for understanding the behavior of these networks. In this paper, we develop a three-dimensional nonaffinity measure capable of providing direct comparison with continuum level homogenized quantities, i.e., strain field. The proposed nonaffinity measure is capable of capturing possible anisotropic microstructures of the filamentous networks. This strain-based nonaffinity measure is used to probe the mechanical behavior at different length scales and investigate the effects of network mechanical and microstructural properties. Specifically, it is found that although all nonaffinity measure components have a power-law variation with the probing length scale, the degree of nonaffinity decreases with increasing the length scale of observation. Furthermore, the amount of nonaffinity is a function of network fiber density, bending stiffness of the constituent filaments, and the network architecture. Finally, it is found that the two power-law scaling regimes previously reported for two-dimensional systems do not appear in three-dimensional networks. Also, unlike two-dimensional models, the exponent of the power-law relation depends weakly on the density of the three-dimensional networks.

  15. Hyaluronan delivery by polymer demixing in polysaccharide-based hydrogels and membranes for biomedical applications.

    PubMed

    Travan, Andrea; Scognamiglio, Francesca; Borgogna, Massimiliano; Marsich, Eleonora; Donati, Ivan; Tarusha, Lorena; Grassi, Mario; Paoletti, Sergio

    2016-10-01

    Alginate-based membranes containing hyaluronic acid (HA) were manufactured by freeze-drying calcium-reticulated hydrogels. The study of the distribution of the two macromolecules within the hydrogel enabled to highlight a polymer demixing mechanism that tends to segregate HA in the external parts of the constructs. Resistance and pliability of the membranes were tuned, while release and degradation studies enabled to quantify the diffusion of both polysaccharides in physiological solution and to measure the viable lifetime of the membranes. Biological studies in vitro proved that the liquid extracts from the HA-containing membranes stimulate wound healing and that fibroblasts are able to colonize the membranes. Overall, such novel alginate-HA membranes represent a promising solution for several medical needs, in particular for wound treatment, giving the possibility to provide an in situ administration of HA from a resorbable device. PMID:27312652

  16. Multiplex lithography for multilevel multiscale architectures and its application to polymer electrolyte membrane fuel cell

    PubMed Central

    Cho, Hyesung; Moon Kim, Sang; Sik Kang, Yun; Kim, Junsoo; Jang, Segeun; Kim, Minhyoung; Park, Hyunchul; Won Bang, Jung; Seo, Soonmin; Suh, Kahp-Yang; Sung, Yung-Eun; Choi, Mansoo

    2015-01-01

    The production of multiscale architectures is of significant interest in materials science, and the integration of those structures could provide a breakthrough for various applications. Here we report a simple yet versatile strategy that allows for the LEGO-like integrations of microscale membranes by quantitatively controlling the oxygen inhibition effects of ultraviolet-curable materials, leading to multilevel multiscale architectures. The spatial control of oxygen concentration induces different curing contrasts in a resin allowing the selective imprinting and bonding at different sides of a membrane, which enables LEGO-like integration together with the multiscale pattern formation. Utilizing the method, the multilevel multiscale Nafion membranes are prepared and applied to polymer electrolyte membrane fuel cell. Our multiscale membrane fuel cell demonstrates significant enhancement of performance while ensuring mechanical robustness. The performance enhancement is caused by the combined effect of the decrease of membrane resistance and the increase of the electrochemical active surface area. PMID:26412619

  17. Multiplex lithography for multilevel multiscale architectures and its application to polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Cho, Hyesung; Moon Kim, Sang; Sik Kang, Yun; Kim, Junsoo; Jang, Segeun; Kim, Minhyoung; Park, Hyunchul; Won Bang, Jung; Seo, Soonmin; Suh, Kahp-Yang; Sung, Yung-Eun; Choi, Mansoo

    2015-09-01

    The production of multiscale architectures is of significant interest in materials science, and the integration of those structures could provide a breakthrough for various applications. Here we report a simple yet versatile strategy that allows for the LEGO-like integrations of microscale membranes by quantitatively controlling the oxygen inhibition effects of ultraviolet-curable materials, leading to multilevel multiscale architectures. The spatial control of oxygen concentration induces different curing contrasts in a resin allowing the selective imprinting and bonding at different sides of a membrane, which enables LEGO-like integration together with the multiscale pattern formation. Utilizing the method, the multilevel multiscale Nafion membranes are prepared and applied to polymer electrolyte membrane fuel cell. Our multiscale membrane fuel cell demonstrates significant enhancement of performance while ensuring mechanical robustness. The performance enhancement is caused by the combined effect of the decrease of membrane resistance and the increase of the electrochemical active surface area.

  18. Multiplex lithography for multilevel multiscale architectures and its application to polymer electrolyte membrane fuel cell.

    PubMed

    Cho, Hyesung; Moon Kim, Sang; Sik Kang, Yun; Kim, Junsoo; Jang, Segeun; Kim, Minhyoung; Park, Hyunchul; Won Bang, Jung; Seo, Soonmin; Suh, Kahp-Yang; Sung, Yung-Eun; Choi, Mansoo

    2015-01-01

    The production of multiscale architectures is of significant interest in materials science, and the integration of those structures could provide a breakthrough for various applications. Here we report a simple yet versatile strategy that allows for the LEGO-like integrations of microscale membranes by quantitatively controlling the oxygen inhibition effects of ultraviolet-curable materials, leading to multilevel multiscale architectures. The spatial control of oxygen concentration induces different curing contrasts in a resin allowing the selective imprinting and bonding at different sides of a membrane, which enables LEGO-like integration together with the multiscale pattern formation. Utilizing the method, the multilevel multiscale Nafion membranes are prepared and applied to polymer electrolyte membrane fuel cell. Our multiscale membrane fuel cell demonstrates significant enhancement of performance while ensuring mechanical robustness. The performance enhancement is caused by the combined effect of the decrease of membrane resistance and the increase of the electrochemical active surface area. PMID:26412619

  19. High resolution neutron imaging of water in the polymer electrolyte fuel cell membrane

    SciTech Connect

    Mukherjee, Partha P; Makundan, Rangachary; Spendelow, Jacob S; Borup, Rodney L; Hussey, D S; Jacobson, D L; Arif, M

    2009-01-01

    Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.

  20. Control of Chemical, Thermal, and Gas Transport Properties in Dense Phosphazene Polymer Membranes.

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart; Mark L. Stone; Mason K. Harrup; Thomas A. Luther; Eric S. Peterson

    2005-10-01

    Polyphosphazenes are hybrid polymers having organic pendant groups attached to an inorganic backbone. Phosphazene polymers can be tailored to specific applications through the attachment of a variety of different pendant groups to the phosphazene backbone. Applications for which these polymers have proven useful include solid polymer electrolytes for batteries and fuel cells, as well as, membranes for gas and liquid separations. In past work, phosphazene polymers have been synthesized using mixtures of pendant groups with differing chemical affinities. Specific ratios of hydrophobic and hydrophilic pendant groups were placed on the phosphazene backbone with a goal of demonstrating control of solubility, and therefore chemical selectivity. In this work, a series of phosphazene homo-polymers were synthesized having varying amounts of hydrophobic and hydrophilic character on each individual pendant group. Polymers were synthesized having a hydrophilic portion next to the polymer backbone and the hydrophobic portion on the terminal end of the pendant group. The effects of these combined hydrophobic/hydrophilic pendant groups on polymer morphology and gas transport properties are presented. The following data will be addressed: thermal characterization, pure gas permeability on seven gases (Ar, H2, O2, N2, CO2, and CH4 ), and ideal selectivity for the gas pairs: O2/N2, H2/CO2, CO2/H2, CO2/CH4 and CO2/N2.

  1. Active Curved Polymers Form Vortex Patterns on Membranes

    NASA Astrophysics Data System (ADS)

    Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

    2016-04-01

    Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation.

  2. Active Curved Polymers Form Vortex Patterns on Membranes.

    PubMed

    Denk, Jonas; Huber, Lorenz; Reithmann, Emanuel; Frey, Erwin

    2016-04-29

    Recent in vitro experiments with FtsZ polymers show self-organization into different dynamic patterns, including structures reminiscent of the bacterial Z ring. We model FtsZ polymers as active particles moving along chiral, circular paths by Brownian dynamics simulations and a Boltzmann approach. Our two conceptually different methods point to a generic phase behavior. At intermediate particle densities, we find self-organization into vortex structures including closed rings. Moreover, we show that the dynamics at the onset of pattern formation is described by a generalized complex Ginzburg-Landau equation. PMID:27176542

  3. Semi-interpenetrating polymer network for tougher and more microcracking resistant high temperature polymers

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor)

    1992-01-01

    This invention is a semi-interpenetrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide. An improved high temperature matrix resin is provided which is capable of performing at 316 C in air for several hundreds of hours. This resin has significantly improved toughness and microcracking resistance, excellent processability and mechanical performance, and cost effectiveness.

  4. Soluble porous coordination polymers by mechanochemistry: from metal-containing films/membranes to active catalysts for aerobic oxidation.

    PubMed

    Zhang, Pengfei; Li, Haiying; Veith, Gabriel M; Dai, Sheng

    2015-01-14

    Soluble porous coordination polymers from mechanochemical synthesis are presented through a coordination polymerization between highly contorted, rigid tetraphenol and a broad variety of transition metal ions. These polymers can be easily cast as metal-containing films or freestanding membranes. Importantly, as-made coordination polymers are highly active and stable in the aerobic oxidation of allylic C-H bonds. PMID:25389070

  5. Mechanism of Actin Network Attachment to Moving Membranes

    PubMed Central

    Co, Carl; Wong, Derek T.; Gierke, Sarah; Chang, Vicky; Taunton, Jack

    2007-01-01

    Summary Actin filament networks exert protrusive and attachment forces on membranes and thereby drive membrane deformation and movement. Here, we show that N-WASP WH2 domains play a previously unanticipated role in vesicle movement by transiently attaching actin filament barbed ends to the membrane. To dissect the attachment mechanism, we reconstituted the propulsive motility of lipid-coated glass beads using purified soluble proteins. N-WASP WH2 mutants assembled actin comet tails and initiated movement, but the comet tails catastrophically detached from the membrane. When presented on the surface of a lipid-coated bead, WH2 domains were sufficient to maintain comet tail attachment. In v-Src-transformed fibroblasts, N-WASP WH2 mutants were severely defective in the formation of circular podosome arrays. In addition to creating an attachment force, interactions between WH2 domains and barbed ends may locally amplify signals for dendritic actin nucleation. PMID:17350575

  6. REVIEW ARTICLE: Network models of fluid, hexatic and polymerized membranes

    NASA Astrophysics Data System (ADS)

    Gompper, G.; Kroll, D. M.

    1997-10-01

    The thermal behaviour of membranes - surfaces of nearly vanishing tension - depends strongly on their internal state, which can be either fluid, crystalline (or polymerized), or hexatic. Thermal fluctuations have a dramatic effect on the conformation and elastic properties of membranes. We describe in this review both the continuum models of membranes which are used for theoretical analyses as well as the network models employed in simulations. The fruitful interaction between these two approaches, which has lead to recent progress in this field, is emphasized. We summarize the essential results of recent research on fluctuating membranes; in particular, the effects of bending rigidity, self-avoidance, attractive interactions, disorder, topological defects and external compression forces are discussed in detail.

  7. Effects of plasticization on ionic conductivity enhancement of crosslinked polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Kyu, Thein; Kyu's Team, Dr.

    Glass transition temperatures (Tg) of solid polymer electrolyte membranes (PEM), comprised of polyethylene glycol diacrylate (PEGDA) prepolymer, lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and succinonitrile (SCN) plasticizer, were systematically examined before and after crosslinking in the isotropic region guided by their ternary phase diagram. With increasing LiTFSI concentration, the Tg of uncured binary PEGDA/LiTFSI mixture increases drastically due to molecular complexation between lithium cation and ether oxygen, but ionic conductivity is very low (<10-6 S cm-1). Upon curing, this Tg increases and further reduces ionic conductivity. Upon adding SCN plasticizer, the Tg of PEM has significantly decreased to -60 oC and ionic conductivity also increased to the superionic conductor level of 10-3 S cm-1. The analysis of ionic conductivity vs. Tg behavior by Vogel-Tamman-Fulcher(VTF) equation revealed that this ionic conductivity enhancement is due to SCN plasticization resulting in lowering the network Tg as well as lowering the activation energy. Supported by NSF-DMR 1161070.

  8. Morphology studies on high-temperature polymer electrolyte membrane fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Mack, Florian; Klages, Merle; Scholta, Joachim; Jörissen, Ludwig; Morawietz, Tobias; Hiesgen, Renate; Kramer, Dominik; Zeis, Roswitha

    2014-06-01

    The electrode morphology influences the properties and performance of polymer electrolyte membrane fuel cells (PEMFC). Here we report our studies of two different electrodes for high-temperature PEMFC prepared by spraying and coating and their impact on the fuel cell performance. Differences in 3D microstructure and adhesion between catalyst layer and gas diffusion layer (GDL) of the electrodes were studied with X-ray microtomography. Scanning electrode microscope investigations show hairline cracks between agglomerates on the surface of the sprayed electrode, whereas the coated electrode shows a network of shrinkage cracks in the catalyst layer. The distribution of the electrode binder polytetrafluoroethylene (PTFE) is related to the locally resolved conductivity, which was determined by scanning the electrode surfaces with a conductive atomic force microscopy (AFM) tip. The macrostructures of the sprayed and coated electrodes are different but contain similar pore structures. The coated electrode has a higher PTFE concentration on the top region, which tends to form a nonconductive and less wettable "skin" on the electrode surface and delays the start-up of the fuel cell. In contrast to low-temperature PEMFC, the electrode morphology has only a minor impact on the steady-state cell performance of high-temperature PEMFC.

  9. High Modulus, High Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation

    NASA Astrophysics Data System (ADS)

    McIntosh, Lucas; Schulze, Morgan; Hillmyer, Marc; Lodge, Timothy

    2014-03-01

    Solvent-free, solid-state polymer electrolyte membranes (PEMs) will play a vital role in next-generation electrochemical devices such as Li-metal batteries and high- T fuel cells. The primary challenge is that these applications require PEMs with substantial mechanical robustness, as well as high ionic conductivity. The key to optimizing orthogonal macroscopic properties is to use a heterogeneous composite with well-defined nanoscopic morphology--specifically, long-range co-continuity of high modulus and ion transport domains, which has proven difficult to achieve in commonly-studied diblock copolymer-based electrolytes. We report a simple synthetic strategy to generate PEMs via polymerization-induced phase separation, where the delicate balance between controlled addition of styrene onto a poly(ethylene oxide) macro-chain transfer agent and simultaneous chemical crosslinking by divinylbenzene results in a disordered structure with domain size of order 10 nm. Crucially, both domains exhibit long-range continuity, which results in PEMs that are glassy solids (modulus ~ 1 GPa) owing to the isotropic network of stiff, crosslinked polystyrene, and are highly conductive (> 1 mS/cm at 70 °C) because ions migrate in channels of low Tg poly(ethylene oxide).

  10. Potentiometric measurement of polymer-membrane electrodes based on lanthanum

    NASA Astrophysics Data System (ADS)

    Saefurohman, Asep; Buchari, Noviandri, Indra; Syoni

    2014-03-01

    Quantitative analysis of rare earth elements which are considered as the standard method that has a high accuracy, and detection limits achieved by the order of ppm is inductively coupled plasma atomic emission spectroscopy (ICPAES). But these tools are expensive and valuable analysis of the high cost of implementation. In this study be made and characterized selective electrode for the determination of rare earth ions is potentiometric. Membrane manufacturing techniques studied is based on immersion (liquid impregnated membrane) in PTFE 0.5 pore size. As ionophores to be used tri butyl phosphate (TBP) and bis(2-etylhexyl) hydrogen phosphate. There is no report previously that TBP used as ionophore in polymeric membrane based lanthanum. Some parameters that affect the performance of membrane electrode such as membrane composition, membrane thickness, and types of membrane materials studied in this research. Manufacturing of Ion Selective Electrodes (ISE) Lanthanum (La) by means of impregnation La membrane in TBP in kerosene solution has been done and showed performance for ISE-La. FTIR spectrum results for PTFE 0.5 pore size which impregnated in TBP and PTFE blank showed difference of spectra in the top 1257 cm-1, 1031 cm-1 and 794.7 cm-1 for P=O stretching and stretching POC from group -OP =O. The result showed shift wave number for P =O stretching of the cluster (-OP=O) in PTFE-TBP mixture that is at the peak of 1230 cm-1 indicated that no interaction bond between hydroxyl group of molecules with molecular clusters fosforil of TBP or R3P = O. The membrane had stable responses in pH range between 1 and 9. Good responses were obtained using 10-3 M La(III) internal solution, which produced relatively high potential. ISE-La showed relatively good performances. The electrode had a response time of 29±4.5 second and could be use for 50 days. The linear range was between 10-5 and 10-1 M.

  11. Potentiometric measurement of polymer-membrane electrodes based on lanthanum

    SciTech Connect

    Saefurohman, Asep Buchari, Noviandri, Indra; Syoni

    2014-03-24

    Quantitative analysis of rare earth elements which are considered as the standard method that has a high accuracy, and detection limits achieved by the order of ppm is inductively coupled plasma atomic emission spectroscopy (ICPAES). But these tools are expensive and valuable analysis of the high cost of implementation. In this study be made and characterized selective electrode for the determination of rare earth ions is potentiometric. Membrane manufacturing techniques studied is based on immersion (liquid impregnated membrane) in PTFE 0.5 pore size. As ionophores to be used tri butyl phosphate (TBP) and bis(2-etylhexyl) hydrogen phosphate. There is no report previously that TBP used as ionophore in polymeric membrane based lanthanum. Some parameters that affect the performance of membrane electrode such as membrane composition, membrane thickness, and types of membrane materials studied in this research. Manufacturing of Ion Selective Electrodes (ISE) Lanthanum (La) by means of impregnation La membrane in TBP in kerosene solution has been done and showed performance for ISE-La. FTIR spectrum results for PTFE 0.5 pore size which impregnated in TBP and PTFE blank showed difference of spectra in the top 1257 cm{sup −1}, 1031 cm{sup −1} and 794.7 cm{sup −1} for P=O stretching and stretching POC from group −OP =O. The result showed shift wave number for P =O stretching of the cluster (−OP=O) in PTFE-TBP mixture that is at the peak of 1230 cm{sup −1} indicated that no interaction bond between hydroxyl group of molecules with molecular clusters fosforil of TBP or R{sub 3}P = O. The membrane had stable responses in pH range between 1 and 9. Good responses were obtained using 10{sup −3} M La(III) internal solution, which produced relatively high potential. ISE-La showed relatively good performances. The electrode had a response time of 29±4.5 second and could be use for 50 days. The linear range was between 10{sup −5} and 10{sup −1} M.

  12. A sacrificial process for fabrication of biodegradable polymer membranes with submicron thickness.

    PubMed

    Beardslee, Luke A; Stolwijk, Judith; Khaladj, Dimitrius A; Trebak, Mohamed; Halman, Justin; Torrejon, Karen Y; Niamsiri, Nuttawee; Bergkvist, Magnus

    2016-08-01

    A new sacrificial molding process using a single mask has been developed to fabricate ultrathin 2-dimensional membranes from several biocompatible polymeric materials. The fabrication process is similar to a sacrificial microelectromechanical systems (MEMS) process flow, where a mold is created from a material that can be coated with a biodegradable polymer and subsequently etched away, leaving behind a very thin polymer membrane. In this work, two different sacrificial mold materials, silicon dioxide (SiO2 ) and Liftoff Resist (LOR) were used. Three different biodegradable materials; polycaprolactone (PCL), poly(lactic-co-glycolic acid) (PLGA), and polyglycidyl methacrylate (PGMA), were chosen as model polymers. We demonstrate that this process is capable of fabricating 200-500 nm thin, through-hole polymer membranes with various geometries, pore-sizes and spatial features approaching 2.5 µm using a mold fabricated via a single contact photolithography exposure. In addition, the membranes can be mounted to support rings made from either SU8 or PCL for easy handling after release. Cell culture compatibility of the fabricated membranes was evaluated with human dermal microvascular endothelial cells (HDMECs) seeded onto the ultrathin porous membranes, where the cells grew and formed confluent layers with well-established cell-cell contacts. Furthermore, human trabecular meshwork cells (HTMCs) cultured on these scaffolds showed similar proliferation as on flat PCL substrates, further validating its compatibility. All together, these results demonstrated the feasibility of our sacrificial fabrication process to produce biocompatible, ultra-thin membranes with defined microstructures (i.e., pores) with the potential to be used as substrates for tissue engineering applications. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1192-1201, 2016. PMID:26079689

  13. Small angle neutron scattering data of polymer electrolyte membranes partially swollen in water

    PubMed Central

    Zhao, Yue; Yoshida, Miru; Oshima, Tatsuya; Koizumi, Satoshi; Rikukawa, Masahiro; Szekely, Noemi; Radulescu, Aurel; Richter, Dieter

    2016-01-01

    In this article, we show the small-angle neutron scattering (SANS) data obtained from the polymer electrolyte membranes (PEMs) equilibrated at a given relative humidity. We apply Hard-Sphere (HS) structure model with Percus–Yervick interference interactions to analyze the dataset. The molecular structure of these PEMs and the morphologies of the fully water-swollen membranes have been elucidated by Zhao et al. “Elucidation of the morphology of the hydrocarbon multi-block copolymer electrolyte membranes for proton exchange fuel cells” [1]. PMID:27054164

  14. Small angle neutron scattering data of polymer electrolyte membranes partially swollen in water.

    PubMed

    Zhao, Yue; Yoshida, Miru; Oshima, Tatsuya; Koizumi, Satoshi; Rikukawa, Masahiro; Szekely, Noemi; Radulescu, Aurel; Richter, Dieter

    2016-06-01

    In this article, we show the small-angle neutron scattering (SANS) data obtained from the polymer electrolyte membranes (PEMs) equilibrated at a given relative humidity. We apply Hard-Sphere (HS) structure model with Percus-Yervick interference interactions to analyze the dataset. The molecular structure of these PEMs and the morphologies of the fully water-swollen membranes have been elucidated by Zhao et al. "Elucidation of the morphology of the hydrocarbon multi-block copolymer electrolyte membranes for proton exchange fuel cells" [1]. PMID:27054164

  15. Perturbations of cellular membranes with synthetic polymers and ultrafast lasers

    NASA Astrophysics Data System (ADS)

    Kelly, Christopher Vaughn-Daigneau

    This dissertation examines the response of the plasma membrane to perturbations by synthetic nanoparticles and ultra-fast laser pulses. Both model membranes and living cells were examined in to characterize membrane disruption and the biological response to perturbation. These studies provide a deeper understanding of cell biology and guide the design of effective nanoparticle- or laser-based therapies, as well as warning about unintended exposure. In regards to membrane disruption by pulsed-laser irradiation, irradiation induced giant plasma membrane vesicles (GPMVs) on the surface of the living cell. This process involved the incorporation of material from the extracellular media into both the cytoplasm and the GPMV as the cell responded to the intense pressure and temperature gradients induced by irradiation and the subsequent cavitation. Further, the cell exposed phosphotidylserine to the exterior surface of the plasma membrane and GPMV and initiated caspase activity. Single particle tracking of 20 nm fluorescent beads within the GPMVs demonstrated a complex, gelatinous structure within the GPMV. In regards to nanoparticle-based perturbations, techniques such as isothermal titration calorimetry and molecular dynamics were used to investigate the relationship between nanoparticle properties and membrane disruption. Molecular dynamics simulations examined the binding of third-generation poly(amidoamine) dendrimers to phosphatidylcholine bilayers as a function on nanoparticle termination and membrane phase. A potential of mean force was calculated and demonstrated that the charged dendrimers bound to the zwitterionic phospholipids with approximately 50% more free energy release than uncharged dendrimers. Further, the difference in dendrimer binding to gel and fluid lipids was largely due to the hydrophobic interactions between the lipid tails and the non-polar dendrimer moieties. Isothermal titration calorimetry examined the heat release upon interaction between

  16. Hydrocarbon-based polymer electrolyte cerium composite membranes for improved proton exchange membrane fuel cell durability

    NASA Astrophysics Data System (ADS)

    Lee, Hyejin; Han, Myungseong; Choi, Young-Woo; Bae, Byungchan

    2015-11-01

    Hydrocarbon-based cerium composite membranes were prepared for proton exchange membrane fuel cell applications to increase oxidative stability. Different amounts of cerium ions were impregnated in sulfonated poly(arylene ether sulfone) (SPES) membranes and their physicochemical properties were investigated according to the cerium content. Field-emission scanning electron microscopy and inductively coupled plasma analyses confirmed the presence of cerium ions in the composite membranes and 1H NMR indicated the successful coordination of sulfonic acid groups with the metal ions. Increasing amounts of cerium ions resulted in decreases in the proton conductivity and water uptake, but enhanced oxidative stability. The oxidative stability of the composite membranes was proven via a hydrogen peroxide exposure experiment which mimicked fuel cell operating conditions. In addition, more than 2200 h was achieved with the composite membrane under in situ accelerated open circuit voltage (OCV) durability testing (DOE protocol), whereas the corresponding pristine SPES membrane attained only 670 h.

  17. Nanomaterials for Polymer Electrolyte Membrane Fuel Cells; Materials Challenges Facing Electrical Energy Storate

    SciTech Connect

    Gopal Rao, MRS Web-Editor; Yury Gogotsi, Drexel University; Karen Swider-Lyons, Naval Research Laboratory

    2010-08-05

    Symposium T: Nanomaterials for Polymer Electrolyte Membrane Fuel Cells Polymer electrolyte membrane (PEM) fuel cells are under intense investigation worldwide for applications ranging from transportation to portable power. The purpose of this seminar is to focus on the nanomaterials and nanostructures inherent to polymer fuel cells. Symposium topics will range from high-activity cathode and anode catalysts, to theory and new analytical methods. Symposium U: Materials Challenges Facing Electrical Energy Storage Electricity, which can be generated in a variety of ways, offers a great potential for meeting future energy demands as a clean and efficient energy source. However, the use of electricity generated from renewable sources, such as wind or sunlight, requires efficient electrical energy storage. This symposium will cover the latest material developments for batteries, advanced capacitors, and related technologies, with a focus on new or emerging materials science challenges.

  18. Ultrathin self-assembled anionic polymer membranes for superfast size-selective separation.

    PubMed

    Deng, Chao; Zhang, Qiu Gen; Han, Guang Lu; Gong, Yi; Zhu, Ai Mei; Liu, Qing Lin

    2013-11-21

    Nanoporous membranes with superior separation performance have become more crucial with increasing concerns in functional nanomaterials. Here novel ultrahigh permeable nanoporous membranes have been fabricated on macroporous supports by self-assembly of anionic polymer on copper hydroxide nanostrand templates in organic solution. This facile approach has a great potential for the fabrication of ultrathin anionic polymer membranes as a general method. The as-fabricated self-assembled membranes have a mean pore size of 5-12 nm and an adjustable thickness as low as 85 nm. They allow superfast permeation of water, and exhibit excellent size-selective separation properties and good fouling resistance for negatively-charged solutes during filtration. The 85 nm thick membrane has an ultrahigh water flux (3306 l m(-2) h(-1) bar(-1)) that is an order of magnitude larger than commercial membranes, and can highly efficiently separate 5 and 15 nm gold nanoparticles from their mixtures. The newly developed nanoporous membranes have a wide application in separation and purification of biomacromolecules and nanoparticles. PMID:24072040

  19. Network and neuronal membrane properties in hybrid networks reciprocally regulate selectivity to rapid thalamocortical inputs.

    PubMed

    Pesavento, Michael J; Pinto, David J

    2012-11-01

    Rapidly changing environments require rapid processing from sensory inputs. Varying deflection velocities of a rodent's primary facial vibrissa cause varying temporal neuronal activity profiles within the ventral posteromedial thalamic nucleus. Local neuron populations in a single somatosensory layer 4 barrel transform sparsely coded input into a spike count based on the input's temporal profile. We investigate this transformation by creating a barrel-like hybrid network with whole cell recordings of in vitro neurons from a cortical slice preparation, embedding the biological neuron in the simulated network by presenting virtual synaptic conductances via a conductance clamp. Utilizing the hybrid network, we examine the reciprocal network properties (local excitatory and inhibitory synaptic convergence) and neuronal membrane properties (input resistance) by altering the barrel population response to diverse thalamic input. In the presence of local network input, neurons are more selective to thalamic input timing; this arises from strong feedforward inhibition. Strongly inhibitory (damping) network regimes are more selective to timing and less selective to the magnitude of input but require stronger initial input. Input selectivity relies heavily on the different membrane properties of excitatory and inhibitory neurons. When inhibitory and excitatory neurons had identical membrane properties, the sensitivity of in vitro neurons to temporal vs. magnitude features of input was substantially reduced. Increasing the mean leak conductance of the inhibitory cells decreased the network's temporal sensitivity, whereas increasing excitatory leak conductance enhanced magnitude sensitivity. Local network synapses are essential in shaping thalamic input, and differing membrane properties of functional classes reciprocally modulate this effect. PMID:22896716

  20. Polymer Dynamics Effects on Solute Transport in Hairy Nanoparticle Membranes

    NASA Astrophysics Data System (ADS)

    Buenning, Eileen; Bilchak, Connor; Durning, Christopher; Benicewicz, Brian; Sokolov, Alexei; Kumar, Sanat

    Molecular transport measurements in matrix-free grafted nanoparticle (MFGNP) films have shown remarkable enhancement of permeability and ideal selectivity of small condensable molecules and simple gases over the neat polymer melts and conventional, dispersed nanoparticle composites. Films comprised of covalently-attached poly(methyl acrylate) PMA chains to the surface of 14nm silica particles self-assemble into ordered arrays, and we postulate this structure plays an important role in regulating solute transport. This self-assembly creates interstitial spaces between the nanoparticle cores, which the polymer chains can only fill by stretching. Here we use small-angle neutron scattering (SANS), broadband dielectric spectroscopy (BDS), rheology and temperature-modulated differential scanning calorimetry (TMDSC) to probe polymer chain and segmental dynamics and investigate this hypothesis of chain stretching in MFGNP materials. We found that grafting slows both chain and segmental relaxation, and increases fragility, indicating that the chains are more ``frustrated'' in the grafted systems. We propose that the effects of the chain/surface interactions on chain dynamics leads to an increase in available free volume and thus enhances transport properties in MFGNP systems. Special thanks to the NSF GRFP and the DOE SCGSR programs.

  1. Scalable fabrication of carbon nanotube/polymer nanocomposite membranes for high flux gas transport.

    PubMed

    Kim, Sangil; Jinschek, Joerg R; Chen, Haibin; Sholl, David S; Marand, Eva

    2007-09-01

    We present a simple, fast, and practical route to vertically align carbon nanotubes on a porous support using a combination of self-assembly and filtration methods. The advantage of this approach is that it can be easily scaled up to large surface areas, allowing the fabrication of membranes for practical gas separation applications. The gas transport properties of thus constructed nanotube/polymer nanocomposite membranes are analogous to those of carbon nanotube membranes grown by chemical vapor deposition. This paper shows the first data for transport of gas mixtures through carbon nanotube membranes. The permeation of gas mixtures through the membranes exhibits different properties than those observed using single-gas experiments, confirming that non-Knudsen transport occurs. PMID:17685662

  2. Ultrathin Polymer Membranes with Patterned, Micrometric Pores for Organs-on-Chips.

    PubMed

    Pensabene, Virginia; Costa, Lino; Terekhov, Alexander Y; Gnecco, Juan S; Wikswo, John P; Hofmeister, William H

    2016-08-31

    The basal lamina or basement membrane (BM) is a key physiological system that participates in physicochemical signaling between tissue types. Its formation and function are essential in tissue maintenance, growth, angiogenesis, disease progression, and immunology. In vitro models of the BM (e.g., Boyden and transwell chambers) are common in cell biology and lab-on-a-chip devices where cells require apical and basolateral polarization. Extravasation, intravasation, membrane transport of chemokines, cytokines, chemotaxis of cells, and other key functions are routinely studied in these models. The goal of the present study was to integrate a semipermeable ultrathin polymer membrane with precisely positioned pores of 2 μm diameter in a microfluidic device with apical and basolateral chambers. We selected poly(l-lactic acid) (PLLA), a transparent biocompatible polymer, to prepare the semipermeable ultrathin membranes. The pores were generated by pattern transfer using a three-step method coupling femtosecond laser machining, polymer replication, and spin coating. Each step of the fabrication process was characterized by scanning electron microscopy to investigate reliability of the process and fidelity of pattern transfer. In order to evaluate the compatibility of the fabrication method with organs-on-a-chip technology, porous PLLA membranes were embedded in polydimethylsiloxane (PDMS) microfluidic devices and used to grow human umbilical vein endothelial cells (HUVECS) on top of the membrane with perfusion through the basolateral chamber. Viability of cells, optical transparency of membranes and strong adhesion of PLLA to PDMS were observed, thus confirming the suitability of the prepared membranes for use in organs-on-a-chip devices. PMID:27513606

  3. Entanglements in polymer networks: two-state invariant

    NASA Astrophysics Data System (ADS)

    Müller-Nedebock, Kristian

    2001-03-01

    At the time of crosslinking of polymer chains, entanglements of these chains become permanent features of the resulting network. In a statistical physics formulation these constraints on the polymers can be dealt with by inclusion of invariants for the entangled states of chains. Analytical results are presented based upon an extension of a variational formalism for mechanical properties of entangled gels with a two-state invariant by Edwards and Müller-Nedebock (J. Phys. A: Math. Gen.32 3301 (1999)). Apart from showing Mooney-Rivlin-like behaviour of the reduced stress the theory is applied to olympic gels and discussed in the context of the limitations due to the approximations in this approach.

  4. Tough, processable semi-interpenetrating polymer networks from monomer reactants

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H. (Inventor)

    1994-01-01

    A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance, and mechanical performance, when compared to the commercial Thermid materials. This simultaneous semi-IPN was prepared by mixing the monomer precursors of Thermid AL-600 (a thermoset) and NR-150B2 (a thermoplastic) and allowing the monomers to react randomly upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene end-capped polyimides which were previously inherently brittle and difficult to process.

  5. Investigation of domain size in polymer membranes using double quantum filtered spin diffusion MAS NMR.

    SciTech Connect

    Fujimoto, Cy H.; Alam, Todd Michael; Cherry, Brian Ray; Cornelius, Christopher James

    2005-02-01

    Solid-state {sup 1}H magic angle spinning (MAS) NMR was used to investigate sulfonated Diels-Alder poly(phenlylene) polymer membranes. Under high spinning speed {sup 1}H MAS conditions, the proton environments of the sulfonic acid and phenylene polymer backbone are resolved. A double-quantum (DQ) filter using the rotor-synchronized back-to-back (BABA) NMR multiple-pulse sequence allowed the selective suppression of the sulfonic proton environment in the {sup 1}H MAS NMR spectra. This DQ filter in conjunction with a spin diffusion NMR experiment was then used to measure the domain size of the sulfonic acid component within the membrane. In addition, the temperature dependence of the sulfonic acid spin-spin relaxation time (T{sub 2}) was determined, providing an estimate of the activation energy for the proton dynamics of the dehydrated membrane.

  6. Reversible Supramolecular Surface Attachment of Enzyme-Polymer Conjugates for the Design of Biocatalytic Filtration Membranes.

    PubMed

    Moridi, Negar; Corvini, Philippe F-X; Shahgaldian, Patrick

    2015-12-01

    To be used successfully in continuous reactor systems, enzymes must either be retained using filtration membranes or immobilized on a solid component of the reactor. Whereas the first approach requires large amounts of energy, the second approach is limited by the low temporal stability of enzymes under operational conditions. To circumvent these major stumbling blocks, we have developed a strategy that enables the reversible supramolecular immobilization of bioactive enzyme-polymer conjugates at the surface of filtration membranes. The polymer is produced through a reversible addition-fragmentation transfer method; it contains multiple adamantyl moieties that are used to bind the resulting conjugate at the surface of the membrane which has surface-immobilized cyclodextrin macrocycles. This supramolecular modification is stable under operational conditions and allows for efficient biocatalysis, and can be reversed by competitive host-guest interactions. PMID:26461451

  7. The casting and mechanism of formation of semi-permeable polymer membranes in a microgravity environment

    NASA Astrophysics Data System (ADS)

    Vera, I.

    The National Electric Company of Venezuela, C.A.D.A.F.E., is sponsoring the development of this experiment which represents Venezuela's first scientific experiment in space. The apparatus for the automatic casting of polymer thin films will be contained in NASA's payload No. G-559 of the Get Away Special program for a future orbital space flight in the U.S. Space Shuttle. Semi-permeable polymer membranes have important applications in a variety of fields, such as medecine, energy, and pharmaceuticals, and in general fluid separation processes such as reverse osmosis, ultra-filtration, and electro-dialysis. The casting of semi-permeable membranes in space will help to identify the roles of convection in determining the strucutre of these membranes.

  8. Electrophoretic concentration of DNA at nanoporous polymer membranes for separations and diagnostics.

    SciTech Connect

    Thaitrong, Numrin; Meagher, Robert J.; Singh, Anup K.

    2010-11-01

    We report on the use of thin ({approx}30 micron) photopatterned polymer membranes for on-line preconcentration of single- or double-stranded DNA samples prior to electrophoretic analysis. Shaped UV laser light is used to quickly ({approx}10 seconds) polymerize a highly crosslinked polyacrylamide plug. By applying an electric field across the membrane, DNA from a dilute sample can be concentrated into a narrow zone (<100 micron wide) at the outside edge of the membrane. The field at the membrane can then be reversed, allowing the narrow plug to be cleanly injected into a separation channel filled with a sieving polymer for analysis. Concentration factors >100 are possible, increasing the sensitivity of analysis for dilute samples. We have fabricated both neutral membranes (purely size-based exclusion) as well as anionic membranes (size and charge exclusion), and characterized the rate of preconcentration as well as the efficiency of injection from both types of membrane, for DNA, ranging from a 20 base ssDNA oligonucleotide to >14 kbp dsDNA. We have also investigated the effects of concentration polarization on device performance for the charged membrane. Advantages of the membrane preconcentration approach include the simplicity of device fabrication and operation, and the generic (non-sequence specific) nature of DNA capture, which is useful for complex or poorly characterized samples where a specific capture sequence is not present. The membrane preconcentration approach is well suited to simple single-level etch glass chips, with no need for patterned electrodes, integrated heaters, valves, or other elements requiring more complex chip fabrication. Additionally, the ability to concentrate multiple charged analytes into a narrow zone enables a variety of assay functionalities, including enzyme-based and hybridization-based analyses.

  9. Surprising high hydrophobicity of polymer networks from hydrophilic components.

    PubMed

    Attanasio, Agnese; Bayer, Ilker S; Ruffilli, Roberta; Ayadi, Farouk; Athanassiou, Athanassia

    2013-06-26

    We report a simple and inexpensive method of fabricating highly hydrophobic novel materials based on interpenetrating networks of polyamide and poly(ethyl cyanoacrylate) hydrophilic components. The process is a single-step solution casting from a common solvent, formic acid, of polyamide and ethyl cyanoacrylate monomers. After casting and subsequent solvent evaporation, the in situ polymerization of ethyl cyanoacrylate monomer forms polyamide-poly(ethyl cyanoacrylate) interpenetrating network films. The interpenetrating networks demonstrate remarkable waterproof properties allowing wettability control by modulating the concentration of the components. In contrast, pure polyamide and poly(ethyl cyanoacrylate) films obtained from formic acid solutions are highly hygroscopic and hydrophilic, respectively. The polymerization of ethyl cyanoacrylate in the presence of polyamide promotes molecular interactions between the components, which reduce the available hydrophilic moieties and render the final material hydrophobic. The wettability, morphology, and thermo-physical properties of the polymeric coatings were characterized. The materials developed in this work take advantage of the properties of both polymers in a single blend and above all, due to their hydrophobic nature and minimal water uptake, can extend the application range of the individual polymers where water repellency is required. PMID:23713478

  10. Covalent Adaptable Networks (CANs): A Unique Paradigm in Crosslinked Polymers

    PubMed Central

    Kloxin, Christopher J.; Scott, Timothy F.; Adzima, Brian J.; Bowman, Christopher N.

    2010-01-01

    Polymer networks possessing reversible covalent crosslinks constitute a novel material class with the capacity for adapting to an externally applied stimulus. These covalent adaptable networks (CANs) represent a trend in polymer network fabrication towards the rational design of structural materials possessing dynamic characteristics for specialty applications. Herein, we discuss the unique attributes of CANs that must be considered when designing, fabricating, and characterizing these smart materials that respond to either thermal or photochemical stimuli. While there are many reversible reactions which to consider as possible crosslink candidates in CANs, there are very few that are readily and repeatedly reversible. Furthermore, characterization of the mechanical properties of CANs requires special consideration owing to their unique attributes. Ultimately, these attributes are what lead to the advantageous properties displayed by CANs, such as recyclability, healability, tunability, shape changes, and low polymerization stress. Throughout this perspective, we identify several trends and future directions in the emerging field of CANs that demonstrate the progress to date as well as the essential elements that are needed for further advancement. PMID:20305795

  11. Progress in the development of interpenetrating polymer network hydrogels

    PubMed Central

    Myung, David; Waters, Dale; Wiseman, Meredith; Duhamel, Pierre-Emile; Noolandi, Jaan; Ta, Christopher N.; Frank, Curtis W.

    2009-01-01

    Interpenetrating polymer networks (IPNs) have been the subject of extensive study since their advent in the 1960s. Hydrogel IPN systems have garnered significant attention in the last two decades due to their usefulness in biomedical applications. Of particular interest are the mechanical enhancements observed in “double network” IPN systems which exhibit nonlinear increases in fracture properties despite being composed of otherwise weak polymers. We have built upon pioneering work in this field as well as in responsive IPN systems to develop an IPN system based on end-linked poly-(ethylene glycol) (PEG) and loosely crosslinked poly(acrylic acid) (PAA) with hydrogen bond-reinforced strain-hardening behavior in water and high initial Young’s moduli under physiologic buffer conditions through osmotically induced pre-stress. Uniaxial tensile tests and equilibrium swelling measurements were used to study PEG/PAA IPN hydrogels having second networks prepared with varying crosslinking and photoinitiator content, pH, solids content, and comonomers. Studies involving the addition of non-ionic comonomers and neutralization of the second network showed that template polymerization appears to be important in the formation of mechanically enhanced IPNs. PMID:19763189

  12. Spectroscopic investigations into degradation of polymer membranes for fuel cells applications

    NASA Astrophysics Data System (ADS)

    Kruczała, Krzysztof; Szczubiałka, Krzysztof; Łańcucki, Łukasz; Zastawny, Izabela; Góra-Marek, Kinga; Dyrek, Krystyna; Sojka, Zbigniew

    2008-05-01

    The research was focused on synthesis of proton conductive, easily degradable polymer membranes, which can be used as a model system to verify the efficiency of transition metal ions (TMI) in prevention of polymer degradation. Two polymers composed of 2-hydroxyethyl methacrylate (HEMA), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), and styrenesulfonic acid (SS) were synthesized. The copolymers were characterized by gel permeation chromatography (GPC), elementary analysis, and FTIR and fluorescence spectroscopies. The results allowed determination of weight-average molecular weight and the copolymer composition. The protons of sulfonic groups were substituted by paramagnetic transition metal ions of various spin states (Cr 3+, S = 3/2 and Mn 2+, S = 5/2) with the loading varying from 0.5 up to 10 mol%. The effectiveness of spin catalysis was checked by EPR. The results obtained indicate enhancement of polymer stability in the presence of Mn 2+.

  13. Immobilization of imidazole moieties in polymer electrolyte composite membrane for elevated temperature fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Ke; Zhou, Bei; Ye, Gongbo; Pan, Mu; Zhang, Haining

    2015-12-01

    Development of membrane electrolyte with reasonable proton conductivity at elevated temperature without external humidification is essential for practical applications of elevated temperature proton exchange membrane fuel cells. Herein, a novel polymer electrolyte composite membrane using imidazole as anhydrous proton carriers for elevated temperature fuel cells is investigated. The imidazole moieties are immobilized inside the Nafion/poly(tetrafluoroethylene) (PTFE) composite membrane through in situ formation of imidazole functionalized silica nanoparticles in Nafion dispersion. The thus-formed membrane exhibits strong Coulombic interaction between negatively charged sulfonic acid groups of Nafion and protonated imidazole moieties, leading to an anhydrous proton conductivity of 0.018 S cm-1 at 180 °C. With the introduction of PTFE matrix, the mechanical strength of the membrane is greatly improved. The peak power density of a single cell assembled from the hybrid membrane is observed to be 130 mW cm-2 under 350 mA cm-2 at 110 °C without external humidification and it remains stable for 20 h continuous operation. The obtained results demonstrate that the developed composite membranes could be utilized as promising membrane electrolytes for elevated temperature fuel cells.

  14. Carbon dioxide separation with a two-dimensional polymer membrane.

    PubMed

    Schrier, Joshua

    2012-07-25

    Carbon dioxide gas separation is important for many environmental and energy applications. Molecular dynamics simulations are used to characterize a two-dimensional hydrocarbon polymer, PG-ES1, that uses a combination of surface adsorption and narrow pores to separate carbon dioxide from nitrogen, oxygen, and methane gases. The CO2 permeance is 3 × 10(5) gas permeation units (GPU). The CO2/N2 selectivity is 60, and the CO2/CH4 selectivity exceeds 500. The combination of high CO2 permeance and selectivity surpasses all known materials, enabling low-cost postcombustion CO2 capture, utilization of landfill gas, and horticulture applications. PMID:22734516

  15. Design of bioabsorbable, amorphous polymer networks and composites

    SciTech Connect

    Wiggins, J.S.

    1992-01-01

    Amorphous, crosslinked, bioabsorbable polymers have been developed as an alternative to conventional linear, semi-crystalline thermoplastic bioabsorbable polymers, and as matrix resins for totally bioabsorbable composites. Bioabsorbable composites have been fabricated, consisting of poly(glycolic acid) surgical mesh embedded in polyester and polyester-urethane based matrices. Low-molecular weight precursors used in the matrices of the composites were based on D, L-lactide and [epsilon]-caprolactone polyols, which were synthesized by coordination ring-opening polymerization using glycol initiators and stannous octoate as catalyst. Polymers initiated with diols were chain extended with fumaric acid for use as unsaturated polyester prepolymers, and were crosslinked using peroxide initiation. Polyester triols synthesized from glycerol initiation were crosslinked with L-lysine diisocyanate (LDI). Networks synthesized from D, L-lactide based precursors were more rigid with higher tensile strengths and moduli, while networks synthesized from [epsilon]-caprolactone were more flexible and elastomeric. Copolymer network properties were influenced by the relative amounts of each monomer incorporated into the copolymers. A composite based on neat poly(D, L-lactide-co-[epsilon]-caprolactone) fumarate displayed a tensile strength of 37 MPa and modulus of 107 MPa; addition of 25 wt% styrene yielded tensile strength and modulus of 64 MPa and 689 MPa, respectively. A silane coupling agent was shown to dramatically improve the fiber-matrix interfacial adhesion; tensile strength of a poly(D, L-lactide-co-glycolic acid) fumarate composite was increased from 84 to 92 MPa upon fiber pretreatment. Improved adhesion was also demonstrated using SEM. DSC revealed that if the glass transitions for the matrices was maintained at [approximately]60[degrees]C, the composites were easily shaped above this temperature, yet remained rigid at biological temperatures.

  16. Self-Healing of Polymer Networks with Reversible Bonds

    NASA Astrophysics Data System (ADS)

    Rubinstein, Michael

    2015-03-01

    Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess nonequilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. The model is extended to describe enhanced toughness of dual networks with both permanent and reversible cross-links. This work was done in collaboration with Drs. Ludwik Leibler, Li-Heng Cai, Evgeny B. Stukalin, N. Arun Kumar and supported by the National Science Foundation.

  17. Conducting interpenetrating polymer network sized to fabricate microactuators

    SciTech Connect

    Khaldi, Alexandre; Plesse, Cedric; Vidal, Frederic; Teyssie, Dominique; Soyer, Caroline; Cattan, Eric; Legrand, Christiane

    2011-04-18

    Interpenetrating polymer networks can become successful actuators in the field of microsystems providing they are compatible with microtechnologies. In this letter, we report on a material synthesized from poly(3,4-ethylenedioxythiophene) and polytetrahydrofuran/poly(ethylene oxide) and microsized by decreasing its thickness to 12 {mu}m and patterning the lateral side using plasma etching at high etch rates and with vertical sidewalls. A chemical process and a 'self degradation' are proposed to explain such etching rates. Preliminary actuation results show that microbeams can move with very large displacements. These microsized actuators are potential candidates in numerous applications, including microswitches, microvalves, microoptical instrumentation, and microrobotics.

  18. Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells

    PubMed Central

    Jeon, Yukwon; Kim, Dong Jun; Koh, Jong Kwan; Ji, Yunseong; Kim, Jong Hak; Shul, Yong-Gun

    2015-01-01

    Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 μm in size, which exhibited a very high power density of 1906 mW/cm2 at 75 °C and Pt loading of 0.4 mg/cm2 with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm2 with an outstanding performance of 1555 mW/cm2 and even at air/low humidity operations. PMID:26552839

  19. Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells.

    PubMed

    Jeon, Yukwon; Kim, Dong Jun; Koh, Jong Kwan; Ji, Yunseong; Kim, Jong Hak; Shul, Yong-Gun

    2015-01-01

    Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 μm in size, which exhibited a very high power density of 1906 mW/cm(2) at 75 °C and Pt loading of 0.4 mg/cm(2) with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm(2) with an outstanding performance of 1555 mW/cm(2) and even at air/low humidity operations. PMID:26552839

  20. Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells

    NASA Astrophysics Data System (ADS)

    Jeon, Yukwon; Kim, Dong Jun; Koh, Jong Kwan; Ji, Yunseong; Kim, Jong Hak; Shul, Yong-Gun

    2015-11-01

    Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 μm in size, which exhibited a very high power density of 1906 mW/cm2 at 75 °C and Pt loading of 0.4 mg/cm2 with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm2 with an outstanding performance of 1555 mW/cm2 and even at air/low humidity operations.

  1. Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries.

    PubMed

    Li, Changyi; Ward, Ashleigh L; Doris, Sean E; Pascal, Tod A; Prendergast, David; Helms, Brett A

    2015-09-01

    Redox flow batteries (RFBs) present unique opportunities for multi-hour electrochemical energy storage (EES) at low cost. Too often, the barrier for implementing them in large-scale EES is the unfettered migration of redox active species across the membrane, which shortens battery life and reduces Coulombic efficiency. To advance RFBs for reliable EES, a new paradigm for controlling membrane transport selectivity is needed. We show here that size- and ion-selective transport can be achieved using membranes fabricated from polymers of intrinsic microporosity (PIMs). As a proof-of-concept demonstration, a first-generation PIM membrane dramatically reduced polysulfide crossover (and shuttling at the anode) in lithium-sulfur batteries, even when sulfur cathodes were prepared as flowable energy-dense fluids. The design of our membrane platform was informed by molecular dynamics simulations of the solvated structures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) vs lithiated polysulfides (Li2Sx, where x = 8, 6, and 4) in glyme-based electrolytes of different oligomer length. These simulations suggested polymer films with pore dimensions less than 1.2-1.7 nm might incur the desired ion-selectivity. Indeed, the polysulfide blocking ability of the PIM-1 membrane (∼0.8 nm pores) was improved 500-fold over mesoporous Celgard separators (∼17 nm pores). As a result, significantly improved battery performance was demonstrated, even in the absence of LiNO3 anode-protecting additives. PMID:26237233

  2. Temperature-controlled interaction of thermosensitive polymer-modified cationic liposomes with negatively charged phospholipid membranes.

    PubMed

    Kono, K; Henmi, A; Takagishi, T

    1999-09-21

    To obtain cationic liposomes of which affinity to negatively charged membranes can be controlled by temperature, cationic liposomes consisting of 3beta-[N-(N', N'-dimethylaminoethane)carbamoyl]cholesterol and dioleoylphosphatidylethanolamine were modified with poly(N-acryloylpyrrolidine), which is a thermosensitive polymer exhibiting a lower critical solution temperature (LCST) at ca. 52 degrees C. The unmodified cationic liposomes did not change its zeta potential between 20-60 degrees C. The polymer-modified cationic liposomes revealed much lower zeta potential values below the LCST of the polymer than the unmodified cationic liposomes. However, their zeta potential increased significantly above this temperature. The unmodified cationic liposomes formed aggregates and fused intensively with anionic liposomes consisting of egg yolk phosphatidylcholine and phosphatidic acid in the region of 20-60 degrees C, due to the electrostatic interaction. In contrast, aggregation and fusion of the polymer-modified cationic liposomes with the anionic liposomes were strongly suppressed below the LCST. However, these interactions were enhanced remarkably above the LCST. In addition, the polymer-modified cationic liposomes did not cause leakage of calcein from the anionic liposomes below the LCST, but promoted the leakage above this temperature as the unmodified cationic liposomes did. Temperature-induced conformational change of the polymer chains from a hydrated coil to a dehydrated globule might affect the affinity of the polymer-modified cationic liposomes to the anionic liposomes. PMID:10561483

  3. Methods for Mapping of Interaction Networks Involving Membrane Proteins

    SciTech Connect

    Hooker, Brian S.; Bigelow, Diana J.; Lin, Chiann Tso

    2007-11-23

    Numerous approaches have been taken to study protein interactions, such as tagged protein complex isolation followed by mass spectrometry, yeast two-hybrid methods, fluorescence resonance energy transfer, surface plasmon resonance, site-directed mutagenesis, and crystallography. Membrane protein interactions pose significant challenges due to the need to solubilize membranes without disrupting protein-protein interactions. Traditionally, analysis of isolated protein complexes by high-resolution 2D gel electrophoresis has been the main method used to obtain an overall picture of proteome constituents and interactions. However, this method is time consuming, labor intensive, detects only abundant proteins and is not suitable for the coverage required to elucidate large interaction networks. In this review, we discuss the application of various methods to elucidate interactions involving membrane proteins. These techniques include methods for the direct isolation of single complexes or interactors as well as methods for characterization of entire subcellular and cellular interactomes.

  4. A novel electro-driven membrane for removal of chromium ions using polymer inclusion membrane under constant D.C. electric current.

    PubMed

    Kaya, Ahmet; Onac, Canan; Alpoguz, H Korkmaz

    2016-11-01

    In this study, the use of polymer inclusion membrane under constant electric current for the removal of Cr(VI) from water has investigated for the first time. Transport of Cr(VI) is performed by an electric current from the donor phase to the acceptor phase with a constant electric current of 0.5A. The optimized membrane includes of 12.1% 2-nitrophenyl octyl ether (2-NPOE), 77.6% cellulose triacetate (CTA), 10.3% tricapryl-methylammonium chloride (Aliquat 336) as a carrier. We tested the applicability of the selected membrane for Cr(VI) removal in real environmental water samples and evaluated its reusability. Electro membrane experiments were carried out under various parameters, such as the effect of electro membrane voltage at constant DC electric current; electro membrane current at constant voltage, acceptor phase pH, and stable electro membrane; and a comparison of polymer inclusion membrane and electro membrane transport studies. The Cr(VI) transport was achieved 98.33% after 40min under optimized conditions. An alternative method has been employed that eliminates the changing of electrical current by the application of constant electric current for higher reproducibility of electro membrane extraction experiments by combining the excellent selective and long-term use features of polymer inclusion membrane. PMID:27239722

  5. Adsorption of water to double-network polymers having a hierarchical structure

    NASA Astrophysics Data System (ADS)

    Tominaga, Taiki; Takata, Shin-ichi; Suzuki, Jun-ichi; Aizawa, Kazuya; Seto, Hideki; Arai, Masatoshi

    2014-04-01

    Double-network hydrogels (DN-gels) have cross-linked aqueous polymer networks which result in unique mechanical properties [1,2]. Although the structure of the hydrophilic polymer networks have been previously determined [3,4,5], it was not clear how water molecules are adsorbed to the polymer network. We prepared freeze-dried DN-gels (DN-polymers) made of polyacrylamide and sodium salt of poly(2-acrylamido-2-methylpropane sulfonic acid), and small-angle neutron scattering (SANS) experiments were conducted to determine the humidity dependence of the nanoscale structure. The SANS results show that water molecules adsorb on larger structures than the mesh size of polymer networks at low relative humidity (RH), and adsorb gradually on the segmental scale of polymers with increasing RH.

  6. Degradation of polymer electrolyte membrane fuel cell by siloxane in biogas

    NASA Astrophysics Data System (ADS)

    Seo, Ji-Sung; Kim, Da-Yeong; Hwang, Sun-Mi; Seo, Min Ho; Seo, Dong-Jun; Yang, Seung Yong; Han, Chan Hui; Jung, Yong-Min; Guim, Hwanuk; Nahm, Kee Suk; Yoon, Young-Gi; Kim, Tae-Young

    2016-06-01

    We studied the degradation and durability of polymer electrolyte membrane fuel cell (PEMFC) at membrane-electrode-assembly (MEA) level by injection of octamethylcyclotetrasiloxane (D4) as a representative siloxane, which has been found in many industrial and personal products. Specifically, i) GC/MS analysis demonstrated that the ring-opening polymerization of D4 could result in the formation of various linear and cyclic siloxanes in both electrodes of MEA; ii) post-test analysis revealed that the transformed siloxanes were transported from the anode to the cathode via free-volumes in the polymer membrane; iii) RDE measurement and DFT calculation revealed that D4 was not directly responsible for the electrocatalytic activity of Pt; iv) electrochemical analysis demonstrated that the residual methyl groups of siloxane and various siloxanes did not hinder the proton transport in the polymer membrane; and v) siloxanes accumulated in the primary and secondary pores with the exception of an external surface of carbon, causing an increase in the oxygen reactant's resistance and resulting in a decrease of the cell performance. In addition, we confirmed that injection of D4 did not affect the carbon corrosion adversely because the siloxane had little influence on water sorption in the catalyst layer.

  7. Novel Zeolitic Imidazolate Framework/Polymer Membranes for Hydrogen Separations in Coal Processing

    SciTech Connect

    Musselman, Inga H.

    2013-01-31

    Nanoparticles of zeolitic imidazolate frameworks and other related hybrid materials were prepared by modifying published synthesis procedures by introducing bases, changing stoichiometric ratios, or adjusting reaction conditions. These materials were stable at temperatures >300 °C and were compatible with the polymer matrices used to prepare mixed-matrix membranes (MMMs). MMMs tested at 300 °C exhibited a >30 fold increase in permeability, compared to those measured at 35 °C, while maintaining H{sub 2}/CO{sub 2} selectivity. Measurements at high pressure (up to 30 atm) and high temperature (up to 300 °C) resulted in an increase in gas flux across the membrane with retention of selectivity. No variations in permeability were observed at high pressures at either 35 or 300 °C. CO{sub 2}-induced plasticization was not observed for Matrimid®, VTEC, and PBI polymers or their MMMs at 30 atm and 300 °C. Membrane surface modification by cross-linking with ethylenediamine resulted in an increase in H{sub 2}/CO{sub 2} selectivity at 35 °C. Spectrometric analysis showed that the cross-linking was effective to temperatures <150 °C. At higher temperatures, the cross-linked membranes exhibit a H2/CO2 selectivity similar to the uncrosslinked polymer.

  8. Identifying the hub proteins from complicated membrane protein network systems.

    PubMed

    Shen, Yi-Zhen; Ding, Yong-Sheng; Gu, Quan; Chou, Kuo-Chen

    2010-05-01

    The so-called "hub proteins" are those proteins in a protein-protein interaction network system that have remarkably higher interaction relations (or degrees) than the others. Therefore, the information of hub proteins can provide very useful insights for selecting or prioritizing targets during drug development. In this paper, by combining the multi-agent-based method with the graphical spectrum analysis and immune-genetic algorithm, a novel simulator for identifying the hub proteins from membrane protein interaction networks is proposed. As a demonstration of using the simulator, two hub membrane proteins, YPL227C and YIL147C, were identified from a complicated network system consisting of 1500 membrane proteins. Meanwhile, along with the two identified hub proteins, their molecular functions, biological processes, and cellular components were also revealed. It is anticipated that the hub-protein-simulator may become a very useful tool for system biology and drug development, particularly in deciphering unknown protein functions, determining protein complexes, and in identifying the key targets from a complicated disease system. PMID:20507268

  9. Time dependent mechanical modeling for polymers based on network theory

    NASA Astrophysics Data System (ADS)

    Billon, Noëlle

    2016-05-01

    Despite of a lot of attempts during recent years, complex mechanical behaviour of polymers remains incompletely modelled, making industrial design of structures under complex, cyclic and hard loadings not totally reliable. The non linear and dissipative viscoelastic, viscoplastic behaviour of those materials impose to take into account non linear and combined effects of mechanical and thermal phenomena. In this view, a visco-hyperelastic, viscoplastic model, based on network description of the material has recently been developed and designed in a complete thermodynamic frame in order to take into account those main thermo-mechanical couplings. Also, a way to account for coupled effects of strain-rate and temperature was suggested. First experimental validations conducted in the 1D limit on amorphous rubbery like PMMA in isothermal conditions led to pretty goods results. In this paper a more complete formalism is presented and validated in the case of a semi crystalline polymer, a PA66 and a PET (either amorphous or semi crystalline) are used. Protocol for identification of constitutive parameters is described. It is concluded that this new approach should be the route to accurately model thermo-mechanical behaviour of polymers using a reduced number of parameters of some physicl meaning.

  10. Influence of lipid membranes rigidity on properties of supporting polymer

    SciTech Connect

    Majewski, Jaroslaw; Singh, Saurabh; Dubey, Manish

    2012-06-18

    The motivation of this study is: (1) Controllable release of cultured cell sheets - (a) NIPAAm is non-toxic and collapsed at physiological Temp, (b) good platform for cell adherence and growth, (c) below polymer transition temp, cultured sheets are released, (d) hydration of matrix possible cause of cell attachment/detachment, (e) need for understanding hydration of underlying support; (2) Matrix elasticity plays an important role in cell lineage specification - (a) matrices of known stiffness are utilized as supports to understand physical effect of in-vivo tissue microenvironment for therapeutic uses of stem cells, (b) it is believed that stem cells 'sense' the elasticity and transduce the information into morphological changes, (c) Imperative to consider the changes induced in matrix as a result of immobilized cells.

  11. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Tavassoli, Arash; Lim, Chan; Kolodziej, Joanna; Lauritzen, Michael; Knights, Shanna; Wang, G. Gary; Kjeang, Erik

    2016-08-01

    Aiming at durability issues of fuel cells, this research is dedicated to a novel experimental approach in the analysis of local membrane degradation phenomena in polymer electrolyte fuel cells, shedding light on the potential effects of manufacturing imperfections on this process. With a comprehensive review on historical failure analysis data from field operated fuel cells, local sources of iron oxide contaminants, catalyst layer cracks, and catalyst layer delamination are considered as potential candidates for initiating or accelerating the local membrane degradation phenomena. Customized membrane electrode assemblies with artificial defects are designed, fabricated, and subjected to membrane accelerated stress tests followed by extensive post-mortem analysis. The results reveal a significant accelerating effect of iron oxide contamination on the global chemical degradation of the membrane, but dismiss local traces of iron oxide as a potential stressor for local membrane degradation. Anode and cathode catalyst layer cracks are observed to have negligible impact on the membrane degradation phenomena. Notably however, distinct evidence is found that anode catalyst layer delamination can accelerate local membrane thinning, while cathode delamination has no apparent effect. Moreover, a substantial mitigating effect for platinum residuals on the site of delamination is observed.

  12. A Review of Molecular-Level Mechanism of Membrane Degradation in the Polymer Electrolyte Fuel Cell

    PubMed Central

    Ishimoto, Takayoshi; Koyama, Michihisa

    2012-01-01

    Chemical degradation of perfluorosulfonic acid (PFSA) membrane is one of the most serious problems for stable and long-term operations of the polymer electrolyte fuel cell (PEFC). The chemical degradation is caused by the chemical reaction between the PFSA membrane and chemical species such as free radicals. Although chemical degradation of the PFSA membrane has been studied by various experimental techniques, the mechanism of chemical degradation relies much on speculations from ex-situ observations. Recent activities applying theoretical methods such as density functional theory, in situ experimental observation, and mechanistic study by using simplified model compound systems have led to gradual clarification of the atomistic details of the chemical degradation mechanism. In this review paper, we summarize recent reports on the chemical degradation mechanism of the PFSA membrane from an atomistic point of view. PMID:24958288

  13. Electric Characteristics of Hybrid Polymer Membranes Composed of Two Lipid Species

    NASA Astrophysics Data System (ADS)

    Oohira, Koji; Toko, Kiyoshi; Akiyama, Hideyuki; Yoshihara, Hiroshi; Yamafuji, Kaoru

    1995-09-01

    Electric characteristics of hybrid polymer membranes composed of two lipid species were studied, where one lipid species is positively charged in aqueous solution and the other is negatively charged. As a result, it was found that the hybrid membranes responded to taste substances in different ways according to the molar mixing ratio of these two kinds of lipids, and also showed different response characteristics from those of the single-lipid membranes. The membranes with the mixing ratio around 50% exhibited the largest responses to HCl (sourness) and monosodium glutamate (umami). Moreover, good quantitative agreements with the observed data on the response electric potential were obtained using a theory describing both the changes in surface electric potential and surface charge density with taste substances.

  14. Synthesis and characterization of polyvinyl alcohol copolymer/phosphomolybdic acid-based crosslinked composite polymer electrolyte membranes

    NASA Astrophysics Data System (ADS)

    Anis, Arfat; Banthia, A. K.; Bandyopadhyay, S.

    Polymer electrolyte membrane fuel cells (PEMFCs) are very promising as future energy source due to their high-energy conversion efficiency and will help to solve the environmental concerns of energy production. Polymer electrolyte membrane (PEM) is recognised as the key element for an efficient PEMFC. Chemically crosslinked composite membranes consisting of a poly(vinyl alcohol-co-vinyl acetate-co-itaconic acid) (PVACO) and phosphomolybdic acid (PMA) have been prepared by solution casting and evaluated as proton conducting polymer electrolytes. The proton conductivity of the membranes is investigated as a function of PMA composition, crosslinking density and temperature. The membranes have also been characterized by FTIR spectroscopy, TGA, AFM and TEM. The proton conductivity of the composite membranes is of the order of 10 -3 S cm -1 and shows better resistance to methanol permeability than Nafion 117 under similar measurement conditions.

  15. Modular and Orthogonal Synthesis of Hybrid Polymers and Networks

    PubMed Central

    Liu, Shuang; Dicker, Kevin T.; Jia, Xinqiao

    2015-01-01

    Biomaterials scientists strive to develop polymeric materials with distinct chemical make-up, complex molecular architectures, robust mechanical properties and defined biological functions by drawing inspirations from biological systems. Salient features of biological designs include (1) repetitive presentation of basic motifs; and (2) efficient integration of diverse building blocks. Thus, an appealing approach to biomaterials synthesis is to combine synthetic and natural building blocks in a modular fashion employing novel chemical methods. Over the past decade, orthogonal chemistries have become powerful enabling tools for the modular synthesis of advanced biomaterials. These reactions require building blocks with complementary functionalities, occur under mild conditions in the presence of biological molecules and living cells and proceed with high yield and exceptional selectivity. These chemistries have facilitated the construction of complex polymers and networks in a step-growth fashion, allowing facile modulation of materials properties by simple variations of the building blocks. In this review, we first summarize features of several types of orthogonal chemistries. We then discuss recent progress in the synthesis of step growth linear polymers, dendrimers and networks that find application in drug delivery, 3D cell culture and tissue engineering. Overall, orthogonal reactions and modulular synthesis have not only minimized the steps needed for the desired chemical transformations but also maximized the diversity and functionality of the final products. The modular nature of the design, combined with the potential synergistic effect of the hybrid system, will likely result in novel hydrogel matrices with robust structures and defined functions. PMID:25572255

  16. Characterization of a polymer-infiltrated ceramic-network material

    PubMed Central

    Corazza, Pedro H.; Zhang, Yu

    2015-01-01

    Objectives To characterize the microstructure and determine some mechanical properties of a polymer-ingfiltrated ceramic-network (PICN) material (Vita Enamic, Vita Zahnfabrik) available for CAD–CAM systems. Methods Specimens were fabricated to perform quantitative and qualitative analyses of the material’s microstructure and to determine the fracture toughness (KIc), density (ρ), Poisson’s ratio (v) and Young’s modulus (E). KIc was determined using V-notched specimens and the short beam toughness method, where bar-shaped specimens were notched and 3-point loaded to fracture. ρ was calculated using Archimedes principle, and v and E were measured using an ultrasonic thickness gauge with a combination of a pulse generator and an oscilloscope. Results Microstructural analyses showed a ceramic- and a polymer-based interpenetrating network. Mean and standard deviation values for the properties evaluated were: KIc = 1.09 ± 0.05 MPa m1/2, ρ = 2.09 ± 0.01 g/cm3, v = 0.23 ± 0.002 and E = 37.95 ± 0.34 GPa. Significance The PICN material showed mechanical properties between porcelains and resin-based composites, reflecting its microstructural components. PMID:24656471

  17. Carbonaceous Nanowire Supports for Polymer Electrolyte Membrane Fuel Cells

    SciTech Connect

    Garzon, Fernando; Wilson, Mahlon; Banham, Dustin; More, Karren Leslie

    2016-01-01

    Carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of well dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings. (C) The Author(s) 2015. Published by ECS.

  18. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    SciTech Connect

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; Ye, Siyu; More, Karren Leslie

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of well dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.

  19. Carbonaceous nanowire supports for polymer electrolyte membrane fuel cells

    DOE PAGESBeta

    Garzon, Fernando H.; Wilson, Mahlon S.; Banham, Dustin; Ye, Siyu; More, Karren Leslie

    2015-12-03

    Here, carbohydrate-dye combinations were used to form ionically-linked soft templates for the formation of polypyrrole nanowire networks. High yields of nanostructured products were obtained using small amounts of low-cost carbohydrate and dye template materials, the majority of which remained encapsulated within the nanowires. Varying the concentration and the two-part ratio of the templates influenced the length and diameter of the nanofiber segments within the nanowire network. Pyrolysis of the nanowires yielded carbonaceous fibers containing nitrogen heteroatoms, as well as convoluted graphitic domains, well suited for supporting Pt nanoparticles. The resulting high density of nucleation sites enabled the formation of wellmore » dispersed, smaller Pt particles compared to commercial catalysts, despite significantly higher support surface loadings.« less

  20. Self-Healing of Unentangled Polymer Networks with Reversible Bonds

    PubMed Central

    Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun; Leibler, Ludwik; Rubinstein, Michael

    2013-01-01

    Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. PMID:24347684

  1. Azobenzene Modified Polymer Electrolyte Membrane for Ion Gating

    NASA Astrophysics Data System (ADS)

    Piedrahita, Camilo; Mballa, Mireille; He, Ruixuan; Kyu, Thein

    By virtue of ion concentration gradient across cell membranes, neuron cells are highly polarized driving electrical potential difference (e.g., Gibbs law). To regulate and control ion movement, living cells have specific channels with gates that are permeable to cations, enabling or excluding them via charge polarity and size. This mechanism for generating and transmitting signals from one neuron to another controls body movement via brain function. By virtue of trans-cis isomerization, azobenzene derivative (AZO) has been heavily sought for ion-gating in biological cells as a means of signal generation and transmission through nervous systems. In this work, PEM consisted of PEGDA/SCN/LiTFSI was modified with AZO derivatives for gating of lithium ions. At low concentrations of azobenzene of 3 wt Supported by NSF-DMR 1502543.

  2. Advanced biomolecular materials based on membrane-protein/polymer complexation

    SciTech Connect

    Smith, G.S.; Nowak, A.; Safinya, C.

    1998-12-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of this project was to apply neutron reflectometry and atomic force microscopy to the study of lipid membranes containing proteins. Standard sample preparation techniques were used to produce thin films of these materials appropriate for these techniques. However, these films were not stable, and a new sample preparation technique was required. Toward this goal, the authors have developed a new capability to produce large, freely suspended films of lipid multi-bilayers appropriate for these studies. This system includes a controlled temperature/humidity oven in which the films 5-cm x 5-cm are remotely drawn. The first neutron scattering experiments were then performed using this oven.

  3. Direct measurement of the critical pore size in a polymer membrane

    NASA Astrophysics Data System (ADS)

    Ilton, Mark; Dimaria, Christian; Dalnoki-Veress, Kari

    The formation of pores is an important process in cellular membranes. Here we use freestanding polymer films as model membranes to study the stability of nucleated pores. Polymer membranes with pores of varying size are patterned using a lithographic technique. The membranes are heated above their glass transition temperature to allow viscous flow to occur. Pores with a radius larger than a critical value grow, while pores smaller than the critical radius are observed to shrink and eventually close. Remarkably, holes that are close enough to the critical radius neither grow nor shrink, even though the film is in the melt state. A simple model which takes into account the energy cost of having additional surface area at the edge of a pore describes the experiments with no free parameters. Biological membranes have an additional energetic cost of forming a pore, which we mimic using a lamellar-forming diblock copolymer. Indeed, we find that the critical pore radius is increased when pore formation is frustrated by molecular architecture.

  4. Membrane-enhanced surface acoustic wave analysis of grafted polymer brushes

    NASA Astrophysics Data System (ADS)

    Brass, David A.; Shull, Kenneth R.

    2008-04-01

    An analysis is developed for the frequency response of a quartz crystal resonator (often referred to as a quartz crystal microbalance) that is modified with a grafted solvent-swollen polymer brush and placed in contact with a membrane capping layer. The shear wave generated at the resonator surface couples into the membrane layer with an efficiency that is strongly dependent on the thickness of the swollen brush layer. As a result, the resonant frequency changes by a maximum amount that is closely approximated by the Sauerbrey shift for the capping layer. The calculated shift substantially decreases for increases in the brush thickness of approximately 10nm, which gives a net frequency response that is extremely sensitive to the degree of swelling of the polymer brush. An optimum capping layer thickness is determined by balancing the Sauerbrey shift against dissipative effects that weaken the crystal resonance. This optimum membrane thickness depends only weakly on the properties of the membrane material and is in the micron range. Detailed multilayer calculations are presented for the specific case of a poly(ethylene glycol) brush swollen with water and brought into contact with an elastomeric water-permeable membrane. These calculations confirm that the method is sensitive to the properties of the brush layer in the experimentally relevant thickness regime. Connections are also made to conceptually simpler two and three layer models of the acoustic impedance of the material systems that are brought into contact with the resonator.

  5. Trypsin immobilization in ordered porous polymer membranes for effective protein digestion.

    PubMed

    Qiao, Juan; Kim, Jin Yong; Wang, Yuan Yuan; Qi, Li; Wang, Fu Yi; Moon, Myeong Hee

    2016-02-01

    Fast and effective protein digestion is a vital process for mass spectrometry (MS) based protein analysis. This study introduces a porous polymer membrane enzyme reactor (PPMER) coupled to nanoflow liquid chromatography-tandem MS (nLC-ESI-MS/MS) for on-line digestion and analysis of proteins. Poly (styrene-co-maleic anhydride) (PS-co-MAn) was fabricated by the breath figure method to make a porous polymer membrane in which the MAn group was covalently bound to enzyme. Based on this strategy, microscale PPMER (μPPMER) was constructed for on-line connection with the nLC-ESI-MS/MS system. Its capability for enzymatic digestion with bovine serum albumin (BSA) was evaluated with varied digestion periods. The on-line proteolysis of BSA and subsequent analysis with μPPMER-nLC-ESI-MS/MS revealed that peptide sequence coverage increased from 10.3% (digestion time 10 min) to 89.1% (digestion time 30 min). μPPMER can efficiently digest proteins due to the microscopic confinement effect, showing its potential application in fast protein identification and protease immobilization. Applications of on-line digestion using μPPMER with human plasma and urinary proteome samples showed that the developed on-line method yielded equivalent or better performance in protein coverage and identified more membrane proteins than the in-solution method. This may be due to easy accommodation of hydrophobic membrane proteins within membrane pores. PMID:26772135

  6. Upgrading low-quality natural gas by means of highly performing polymer membranes

    SciTech Connect

    Stern, S.A.

    1995-04-01

    The objective of the present study is to assess the potential usefulness of membrane separation processes for removing acid gases (CO{sub 2} and H{sub 2}S) from low-quality natural gas. Nonporous {open_quotes}dense{close_quotes} (homogeneous) membranes made from new, highly gas-selective polymers are being evaluated for this purpose. The project comprises gas permeability and separation measurements with CH{sub 4}/CO{sub 2} and CH{sub 4}/CO{sub 2}/H{sub 2}S mixtures having compositions in ranges found in low-quality natural gas. Process design studies and economic evaluations are also being made to determine the cost of upgrading low-quality natural gas with the most promising membranes. Until recently, the membranes used in this study were made from new types of polyimides synthesized in our laboratory. The polyimide membranes were found to exhibit a very high CO{sub 2}/CH{sub 4} selectivity but a relatively low H{sub 2}S/CH{sub 4} selectivity. Therefore, different types of polymers that exhibit a high H{sub 2}S/CH{sub 4} selectivity are also being evaluated.

  7. Silicone Membranes to Inhibit Water Uptake into Thermoset Polyurethane Shape-Memory Polymer Conductive Composites

    PubMed Central

    Yu, Ya-Jen; Infanger, Stephen; Grunlan, Melissa A.; Maitland, Duncan J.

    2014-01-01

    Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (Tg) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this study, a silicone membrane was used to inhibit water uptake into a thermoset SMP composite containing conductive filler. Thermoset polyurethane (PU) SMPs were loaded with either 5 wt% carbon black (CB) or 5 wt% carbon nanotubes (CNT) and subsequently coated with either an Al2O3- or silica-filled silicone membrane. It was observed that the silicone membranes, particularly the silica-filled membrane, reduced the rate of water absorption (37 °C) and subsequent Tg depression versus uncoated composites. In turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37 °C. PMID:25663711

  8. Biodegradation test of SPS-LS blends as polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Putri, Zufira; Arcana, I. Made

    2014-03-01

    Sulfonated polystyrene (SPS) can be applied as a proton exchange membrane fuel cell due to its fairly good chemical stability. In order to be applied as polymer electrolyte membrane fuel cells (PEMFCs), membrane polymer should have a good ionic conductivity, high proton conductivity, and high mechanical strength. Lignosulfonate (LS) is a complex biopolymer which has crosslinks and sulfonate groups. SPS-LS blends with addition of SiO2 are used to increase the proton conductivity and to improve the mechanical properties and thermal stability. However, the biodegradation test of SPS-LS blends is required to determine whether the application of these membranes to be applied as an environmentally friendly membrane. In this study, had been done the synthesis of SPS, biodegradability test of SPS-LS blends with variations of LS and SiO2 compositions. The biodegradation test was carried out in solid medium of Luria Bertani (LB) with an activated sludge used as a source of microorganism at incubation temperature of 37°C. Based on the results obtained indicated that SPS-LS-SiO2 blends are more decomposed by microorganism than SPS-LS blends. This result is supported by analysis of weight reduction percentage, functional groups with Fourier Transform Infrared (FTIR) Spectroscopy, and morphological surface with Scanning Electron Microscopy (SEM).

  9. Biodegradation test of SPS-LS blends as polymer electrolyte membrane fuel cells

    SciTech Connect

    Putri, Zufira E-mail: arcana@chem.itb.ac.id; Arcana, I Made E-mail: arcana@chem.itb.ac.id

    2014-03-24

    Sulfonated polystyrene (SPS) can be applied as a proton exchange membrane fuel cell due to its fairly good chemical stability. In order to be applied as polymer electrolyte membrane fuel cells (PEMFCs), membrane polymer should have a good ionic conductivity, high proton conductivity, and high mechanical strength. Lignosulfonate (LS) is a complex biopolymer which has crosslinks and sulfonate groups. SPS-LS blends with addition of SiO{sub 2} are used to increase the proton conductivity and to improve the mechanical properties and thermal stability. However, the biodegradation test of SPS-LS blends is required to determine whether the application of these membranes to be applied as an environmentally friendly membrane. In this study, had been done the synthesis of SPS, biodegradability test of SPS-LS blends with variations of LS and SiO{sub 2} compositions. The biodegradation test was carried out in solid medium of Luria Bertani (LB) with an activated sludge used as a source of microorganism at incubation temperature of 37°C. Based on the results obtained indicated that SPS-LS-SiO{sub 2} blends are more decomposed by microorganism than SPS-LS blends. This result is supported by analysis of weight reduction percentage, functional groups with Fourier Transform Infrared (FTIR) Spectroscopy, and morphological surface with Scanning Electron Microscopy (SEM)

  10. Chelating polymer modified P84 nanofiltration (NF) hollow fiber membranes for high efficient heavy metal removal.

    PubMed

    Gao, Jie; Sun, Shi-Peng; Zhu, Wen-Ping; Chung, Tai-Shung

    2014-10-15

    High performance nanofiltration (NF) membranes for heavy metal removal have been molecularly designed by adsorption of chelating polymers containing negatively charged functional groups such as poly (acrylic acid-co-maleic acid) (PAM), poly (acrylic acid) (PAA) and poly (dimethylamine-co-epichlorohydrin-co-ethylenediamine) (PDMED) on the positively charged polyethyleneimine (PEI) cross-linked P84 hollow fiber substrates. Not only do these chelating polymers change the membrane surface charge and pore size, but also provide an extra mean to remove heavy metal ions through adsorption in addition to traditional steric effect and Donnan exclusion. The adsorbed membranes have comparable water permeability and superior rejections to heavy metals, for instance, Pb(NO3)2, CuSO4, NiCl2, CdCl2, ZnCl2, Na2Cr2O7 and Na2HAsO4, with rejections higher than 98%. The membranes also display excellent rejections to mixed ions with rejections more than 99%. The newly developed membranes show reasonably stability during 60-h tests as well as multiple washes. PMID:25016298

  11. Development of polymer membranes with improved haemocompatibility for biohybrid organ technology.

    PubMed

    Groth, T; Seifert, B; Albrecht, W; Malsch, G; Gross, U; Fey-Lamprecht, F; Michanetzis, G; Missirlis, Y; Engbers, G

    2005-01-01

    Biomedical technology has opened up possibilities of treating the failure of internal organs like kidney and liver by artificial organ therapy. Most of these techniques are based on polymer membranes, which allow the removal of excess of water, salts and toxins from the circulation. However, haemodialysis for the replacement of kidney function results in an increased morbidity and mortality of patients after long-term application. Conventional therapy, such as haemofiltration for the treatment of acute liver failure does not improve significantly the survival rate of patients. Biohybrid organ support as a combination of the artificial organ therapy with the functional activity of immobilised cells seems to be a solution of the problem. Membranes applied in these devices have to face both tissue cells and blood. Organ cells in biohybrid organs have to make intimate contact with the surface of membrane but must also develop close cell-cell-connections as a prerequisite for their survival and high functional activity. Blood to be detoxified will contact the other side of membrane and may not become activated by the synthetic material. New polymer membranes based on acrylonitrile were developed to address these requirements by tailoring the composition of copolymers and to be applied in a specific hollow fibre bioreactor with an outer fibre for blood contact, and an inner fibre for tissue contact or vice versa. PMID:15764821

  12. The Effect of Covalently-Attached ATRP-Synthesized Polymers on Membrane Stability and Cytoprotection in Human Erythrocytes

    PubMed Central

    Clafshenkel, William P.; Murata, Hironobu; Andersen, Jill; Creeger, Yehuda; Russell, Alan J.

    2016-01-01

    Erythrocytes have been described as advantageous drug delivery vehicles. In order to ensure an adequate circulation half-life, erythrocytes may benefit from protective enhancements that maintain membrane integrity and neutralize oxidative damage of membrane proteins that otherwise facilitate their premature clearance from circulation. Surface modification of erythrocytes using rationally designed polymers, synthesized via atom-transfer radical polymerization (ATRP), may further expand the field of membrane-engineered red blood cells. This study describes the fate of ATRP-synthesized polymers that were covalently attached to human erythrocytes as well as the effect of membrane engineering on cell stability under physiological and oxidative conditions in vitro. The biocompatible, membrane-reactive polymers were homogenously retained on the periphery of modified erythrocytes for at least 24 hours. Membrane engineering stabilized the erythrocyte membrane and effectively neutralized oxidative species, even in the absence of free-radical scavenger-containing polymers. The targeted functionalization of Band 3 protein by NHS-pDMAA-Cy3 polymers stabilized its monomeric form preventing aggregation in the presence of the crosslinking reagent, bis(sulfosuccinimidyl)suberate (BS3). A free radical scavenging polymer, NHS-pDMAA-TEMPO˙, provided additional protection of surface modified erythrocytes in an in vitro model of oxidative stress. Preserving or augmenting cytoprotective mechanisms that extend circulation half-life is an important consideration for the use of red blood cells for drug delivery in various pathologies, as they are likely to encounter areas of imbalanced oxidative stress as they circuit the vascular system. PMID:27331401

  13. Quasi-in situ neutron tomography on polymer electrolyte membrane fuel cell stacks

    NASA Astrophysics Data System (ADS)

    Manke, I.; Hartnig, Ch.; Grünerbel, M.; Kaczerowski, J.; Lehnert, W.; Kardjilov, N.; Hilger, A.; Banhart, J.; Treimer, W.; Strobl, M.

    2007-04-01

    Quasi-in situ neutron tomography is applied to polymer electrolyte membrane fuel cell stacks for a cell-by-cell detection of liquid water agglomerates. Water distributions in the corresponding anodic and cathodic flow fields are analyzed separately. The influence of the membrane thickness as well as effects of the electro-osmotic drag and of back-diffusion from the cathode to the anode on the water distribution are investigated. Furthermore, the well-known engineering problem of the anomalous behavior of the outermost cells in long multistacks is addressed. The suitability of neutron tomography to support the development of fuel cells is shown.

  14. Superconducting nanowire networks formed on nanoporous membrane substrates

    NASA Astrophysics Data System (ADS)

    Luo, Qiong

    Introducing a regular array of holes into superconducting thin films has been actively pursued to stabilize and pin the vortex lattice against external driving forces, enabling higher current capabilities. If the width of the sections between neighboring holes is comparable to the superconducting coherence length, the circulation of the Cooper pairs in around the holes in the presence of a magnetic field can also produce the Little-Parks effect, i.e. periodic oscillation of the critical temperature. These two mechanisms, commensurate vortex pinning enhancement by the hole-array and the critical temperature oscillations of a wire network due to Little-Parks effect can induce similar experimental observations such as magnetoresistance oscillation and enhancement of the critical current at specific magnetic fields. This dissertation work investigates the effect of a hole-array on the properties of superconducting films deposited onto nanoporous substrates. Experiments on anisotropies of the critical temperature for niobium films on anodic aluminum oxide membrane substrates containing a regular hole-array reveal that the critical temperature exhibits two strong anisotropic effects: Little-Parks oscillations whose period varies with field direction superimposed on a smooth background arising from one dimensional confinement by the finite lateral space between neighboring holes. The two components of the anisotropy are intrinsically linked and appear in concert. That is, the hole-array changes the dimensionality of a two-dimensional (2D) film to a network of 1D nanowire network. Network of superconducting nanowires with transverse dimensions as small as few nanometers were achieved by coating molybdenum germanium (MoGe) layer onto commercially available filtration membranes which have extremely dense nanopores. The magnetoresistance, magnetic field dependence of the critical temperature and the anisotropies of the synthesized MoGe nanowire networks can be consistently

  15. Lithium dendrite growth through solid polymer electrolyte membranes

    NASA Astrophysics Data System (ADS)

    Harry, Katherine; Schauser, Nicole; Balsara, Nitash

    2015-03-01

    Replacing the graphite-based anode in current batteries with a lithium foil will result in a qualitative increase in the energy density of lithium batteries. The primary reason for not adopting lithium-foil anodes is the formation of dendrites during cell charging. In this study, stop-motion X-ray microtomography experiments were used to directly monitor the growth of lithium dendrites during electrochemical cycling of symmetric lithium-lithium cells with a block copolymer electrolyte. In an attempt to understand the relationship between viscoelastic properties of the electrolyte on dendrite formation, a series of complementary experiments including cell cycling, tomography, ac impedance, and rheology, were conducted above and below the glass transition temperature of the non-conducting poly(styrene) block; the conducting phase is a mixture of rubbery poly(ethylene oxide) and a lithium salt. The tomography experiments enable quantification of the evolution of strain in the block copolymer electrolyte. Our work provides fundamental insight into the dynamics of electrochemical deposition of metallic films in contact with high modulus polymer electrolytes. Rational approaches for slowing down and, perhaps, eliminating dendrite growth are proposed.

  16. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO4 for lithium ion battery application

    NASA Astrophysics Data System (ADS)

    Nurhadini, Arcana, I. Made

    2015-09-01

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO4 membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10-4 S/cm was observed in SA/PEO/LiClO4 membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  17. Synthesis of polymer electrolyte membranes from cellulose acetate/poly(ethylene oxide)/LiClO{sub 4} for lithium ion battery application

    SciTech Connect

    Nurhadini, Arcana, I Made

    2015-09-30

    This study was conducted to determine the effect of cellulose acetate on poly(ethylene oxide)-LiClO{sub 4} membranes as the polymer electrolyte. Cellulose acetate is used as an additive to increase ionic conductivity and mechanical property of polymer electrolyte membranes. The increase the percentage of cellulose acetate in membranes do not directly effect on the ionic conductivity, and the highest ionic conductivity of membranes about 5,7 × 10{sup −4} S/cm was observed in SA/PEO/LiClO{sub 4} membrane with cellulose ratio of 10-25% (w/w). Cellulose acetate in membranes increases mechanical strength of polymer electrolyte membranes. Based on TGA analysis, this polymer electrolyte thermally is stable until 270 °C. The polymer electrolyte membrane prepared by blending the cellulose acetate, poly(ethylene oxide), and lithium chlorate could be potentially used as a polymer electrolyte for lithium ion battery application.

  18. An overview of polymer electrolyte membrane electrolyzer for hydrogen production: Modeling and mass transport

    NASA Astrophysics Data System (ADS)

    Abdol Rahim, A. H.; Tijani, Alhassan Salami; Kamarudin, S. K.; Hanapi, S.

    2016-03-01

    Polymer electrolyte membrane electrolyzer (PEME) is a candidate for advanced engineering technology. There are many polymer electrolyte membrane fuel cell (PEMFC) models that have been reported, but none regarding PEME. This paper presents state of the art mass transport models applied to PEME, a detailed literature review of these models and associate methods have been conducted. PEME models are typically developed using analytical, semi empirical and mechanistic techniques that are based on their state and spatial dimensions. Methods for developing the PEME models are introduced and briefly explained. Furthermore the model cell voltage of PEME, which consists of Nernst voltage, ohmic over potential, activation over potential, and diffusion over potential is discussed with focus on mass transport modeling. This paper also presents current issues encountered with PEME model.

  19. Sulfonated Poly(Ether-Ether-Ketone) Polymer Membranes for Fuel Cells

    NASA Astrophysics Data System (ADS)

    Hodakovska, J.; Kleperis, J.

    2008-01-01

    In the work, sulfonated poly(ether-ether-ketone) (SPEEK) ionomers were synthesized using an original (submitted for patent) and simple method. The resulting membranes were tested to determine parameters that are important for the use of this material in fuel cells (water absorption, sulfonation degree, conductivity, etc.). The thermo-gravimetric analysis has shown a good thermal stability in the range from RT to 200-220 °C, and two characteristic regions of weight loss - 7.4% at ~140 °C (reversible water loss) and 10.3% at 200-220 °C (due to polymer degradation when cross-linked polymer chains permanently break down and their SO3H-groups are lost). The conductivity values obtained by the through-plane measurements of SPEEK membranes were 12 mS/cm at RT and 23 mS/cm at 80 °C.

  20. Multiscale modeling of droplet interface bilayer membrane networks.

    PubMed

    Freeman, Eric C; Farimani, Amir B; Aluru, Narayana R; Philen, Michael K

    2015-11-01

    Droplet interface bilayer (DIB) networks are considered for the development of stimuli-responsive membrane-based materials inspired by cellular mechanics. These DIB networks are often modeled as combinations of electrical circuit analogues, creating complex networks of capacitors and resistors that mimic the biomolecular structures. These empirical models are capable of replicating data from electrophysiology experiments, but these models do not accurately capture the underlying physical phenomena and consequently do not allow for simulations of material functionalities beyond the voltage-clamp or current-clamp conditions. The work presented here provides a more robust description of DIB network behavior through the development of a hierarchical multiscale model, recognizing that the macroscopic network properties are functions of their underlying molecular structure. The result of this research is a modeling methodology based on controlled exchanges across the interfaces of neighboring droplets. This methodology is validated against experimental data, and an extension case is provided to demonstrate possible future applications of droplet interface bilayer networks. PMID:26594262

  1. Droplet formation and growth inside a polymer network: A molecular dynamics simulation study.

    PubMed

    Jung, Jiyun; Jang, Eunseon; Shoaib, Mahbubul Alam; Jo, Kyubong; Kim, Jun Soo

    2016-04-01

    We present a molecular dynamics simulation study that focuses on the formation and growth of nanoscale droplets inside polymer networks. Droplet formation and growth are investigated by the liquid-vapor phase separation of a dilute Lennard-Jones (LJ) fluid inside regularly crosslinked, polymer networks with varying mesh sizes. In a polymer network with small mesh sizes, droplet formation can be suppressed, the extent of which is dependent on the attraction strength between the LJ particles. When droplets form in a polymer network with intermediate mesh sizes, subsequent growth is significantly slower when compared with that in bulk without a polymer network. Interestingly, droplet growth beyond the initial nucleation stage occurs by different mechanisms depending on the mesh size: droplets grow mainly by diffusion and coalescence inside polymer networks with large mesh sizes (as observed in bulk), whereas Ostwald ripening becomes a more dominant mechanism for droplet growth for small mesh sizes. The analysis of droplet trajectories clearly reveals the obstruction effect of the polymer network on the movement of growing droplets, which leads to Ostwald ripening of droplets. This study suggests how polymer networks can be used to control the growth of nanoscale droplets. PMID:27059575

  2. Droplet formation and growth inside a polymer network: A molecular dynamics simulation study

    NASA Astrophysics Data System (ADS)

    Jung, Jiyun; Jang, Eunseon; Shoaib, Mahbubul Alam; Jo, Kyubong; Kim, Jun Soo

    2016-04-01

    We present a molecular dynamics simulation study that focuses on the formation and growth of nanoscale droplets inside polymer networks. Droplet formation and growth are investigated by the liquid-vapor phase separation of a dilute Lennard-Jones (LJ) fluid inside regularly crosslinked, polymer networks with varying mesh sizes. In a polymer network with small mesh sizes, droplet formation can be suppressed, the extent of which is dependent on the attraction strength between the LJ particles. When droplets form in a polymer network with intermediate mesh sizes, subsequent growth is significantly slower when compared with that in bulk without a polymer network. Interestingly, droplet growth beyond the initial nucleation stage occurs by different mechanisms depending on the mesh size: droplets grow mainly by diffusion and coalescence inside polymer networks with large mesh sizes (as observed in bulk), whereas Ostwald ripening becomes a more dominant mechanism for droplet growth for small mesh sizes. The analysis of droplet trajectories clearly reveals the obstruction effect of the polymer network on the movement of growing droplets, which leads to Ostwald ripening of droplets. This study suggests how polymer networks can be used to control the growth of nanoscale droplets.

  3. Numerical evaluation of crack growth in polymer electrolyte fuel cell membranes based on plastically dissipated energy

    NASA Astrophysics Data System (ADS)

    Ding, Guoliang; Santare, Michael H.; Karlsson, Anette M.; Kusoglu, Ahmet

    2016-06-01

    Understanding the mechanisms of growth of defects in polymer electrolyte membrane (PEM) fuel cells is essential for improving cell longevity. Characterizing the crack growth in PEM fuel cell membrane under relative humidity (RH) cycling is an important step towards establishing strategies essential for developing more durable membrane electrode assemblies (MEA). In this study, a crack propagation criterion based on plastically dissipated energy is investigated numerically. The accumulation of plastically dissipated energy under cyclical RH loading ahead of the crack tip is calculated and compared to a critical value, presumed to be a material parameter. Once the accumulation reaches the critical value, the crack propagates via a node release algorithm. From the literature, it is well established experimentally that membranes reinforced with expanded polytetrafluoroethylene (ePTFE) reinforced perfluorosulfonic acid (PFSA) have better durability than unreinforced membranes, and through-thickness cracks are generally found under the flow channel regions but not land regions in unreinforced PFSA membranes. We show that the proposed plastically dissipated energy criterion captures these experimental observations and provides a framework for investigating failure mechanisms in ionomer membranes subjected to similar environmental loads.

  4. Zwitterionic polymer functionalization of polysulfone membrane with improved antifouling property and blood compatibility by combination of ATRP and click chemistry.

    PubMed

    Xiang, Tao; Lu, Ting; Xie, Yi; Zhao, Wei-Feng; Sun, Shu-Dong; Zhao, Chang-Sheng

    2016-08-01

    The chemical compositions are very important for designing blood-contacting membranes with good antifouling property and blood compatibility. In this study, we propose a method combining ATRP and click chemistry to introduce zwitterionic polymer of poly(sulfobetaine methacrylate) (PSBMA), negatively charged polymers of poly(sodium methacrylate) (PNaMAA) and/or poly(sodium p-styrene sulfonate) (PNaSS), to improve the antifouling property and blood compatibility of polysulfone (PSf) membranes. Attenuated total reflectance-Fourier transform infrared spectra, X-ray photoelectron spectroscopy and water contact angle results confirmed the successful grafting of the functional polymers. The antifouling property and blood compatibility of the modified membranes were systematically investigated. The zwitterionic polymer (PSBMA) grafted membranes showed good resistance to protein adsorption and bacterial adhesion; the negatively charged polymer (PNaSS or PNaMAA) grafted membranes showed improved blood compatibility, especially the anticoagulant property. Moreover, the PSBMA/PNaMAA modified membrane showed both antifouling property and anticoagulant property, and exhibited a synergistic effect in inhibiting blood coagulation. The functionalization of membrane surfaces by a combination of ATRP and click chemistry is demonstrated as an effective route to improve the antifouling property and blood compatibility of membranes in blood-contact. PMID:27039977

  5. Copper-catalyzed azide alkyne cycloaddition polymer networks

    NASA Astrophysics Data System (ADS)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  6. Fluorescence energy transfer in quantum dot/azo dye complexes in polymer track membranes

    NASA Astrophysics Data System (ADS)

    Gromova, Yulia A.; Orlova, Anna O.; Maslov, Vladimir G.; Fedorov, Anatoly V.; Baranov, Alexander V.

    2013-10-01

    Fluorescence resonance energy transfer in complexes of semiconductor CdSe/ZnS quantum dots with molecules of heterocyclic azo dyes, 1-(2-pyridylazo)-2-naphthol and 4-(2-pyridylazo) resorcinol, formed at high quantum dot concentration in the polymer pore track membranes were studied by steady-state and transient PL spectroscopy. The effect of interaction between the complexes and free quantum dots on the efficiency of the fluorescence energy transfer and quantum dot luminescence quenching was found and discussed.

  7. DETERMINATION OF THE MASS TRANSFER CHARACTERIZATION OF A CERAMIC-POLYMER COMPOSITE MEMBRANE IN THE PERVAPORATION MODE

    EPA Science Inventory

    The effect of the coating layer thickness on VOC extraction performance of a ceramic polymer composite membrane has been investigated. It was found, under experimental condiitons representing typical field operation, the overall mass transfer rates of feed components were control...

  8. Large enhancement in neurite outgrowth on a cell membrane-mimicking conducting polymer.

    PubMed

    Zhu, Bo; Luo, Shyh-Chyang; Zhao, Haichao; Lin, Hsing-An; Sekine, Jun; Nakao, Aiko; Chen, Chi; Yamashita, Yoshiro; Yu, Hsiao-Hua

    2014-01-01

    Although electrically stimulated neurite outgrowth on bioelectronic devices is a promising means of nerve regeneration, immunogenic scar formation can insulate electrodes from targeted cells and tissues, thereby reducing the lifetime of the device. Ideally, an electrode material capable of electrically interfacing with neurons selectively and efficiently would be integrated without being recognized by the immune system and minimize its response. Here we develop a cell membrane-mimicking conducting polymer possessing several attractive features. This polymer displays high resistance towards nonspecific enzyme/cell binding and recognizes targeted cells specifically to allow intimate electrical communication over long periods of time. Its low electrical impedance relays electrical signals efficiently. This material is capable to integrate biochemical and electrical stimulation to promote neural cellular behaviour. Neurite outgrowth is enhanced greatly on this new conducting polymer; in addition, electrically stimulated secretion of proteins from primary Schwann cells can also occur on it. PMID:25060339

  9. Large enhancement in neurite outgrowth on a cell membrane-mimicking conducting polymer

    NASA Astrophysics Data System (ADS)

    Zhu, Bo; Luo, Shyh-Chyang; Zhao, Haichao; Lin, Hsing-An; Sekine, Jun; Nakao, Aiko; Chen, Chi; Yamashita, Yoshiro; Yu, Hsiao-Hua

    2014-07-01

    Although electrically stimulated neurite outgrowth on bioelectronic devices is a promising means of nerve regeneration, immunogenic scar formation can insulate electrodes from targeted cells and tissues, thereby reducing the lifetime of the device. Ideally, an electrode material capable of electrically interfacing with neurons selectively and efficiently would be integrated without being recognized by the immune system and minimize its response. Here we develop a cell membrane-mimicking conducting polymer possessing several attractive features. This polymer displays high resistance towards nonspecific enzyme/cell binding and recognizes targeted cells specifically to allow intimate electrical communication over long periods of time. Its low electrical impedance relays electrical signals efficiently. This material is capable to integrate biochemical and electrical stimulation to promote neural cellular behaviour. Neurite outgrowth is enhanced greatly on this new conducting polymer; in addition, electrically stimulated secretion of proteins from primary Schwann cells can also occur on it.

  10. Highly Conductive Anion-Exchange Membranes from Microporous Tröger's Base Polymers.

    PubMed

    Yang, Zhengjin; Guo, Rui; Malpass-Evans, Richard; Carta, Mariolino; McKeown, Neil B; Guiver, Michael D; Wu, Liang; Xu, Tongwen

    2016-09-12

    The development of polymeric anion-exchange membranes (AEMs) combining high ion conductivity and long-term stability is a major challenge for materials chemistry. AEMs with regularly distributed fixed cationic groups, based on the formation of microporous polymers containing the V-shape rigid Tröger's base units, are reported for the first time. Despite their simple preparation, which involves only two synthetic steps using commercially available precursors, the polymers provide AEMs with exceptional hydroxide conductivity at relatively low ion-exchange capacity, as well as a high swelling resistance and chemical stability. An unprecedented hydroxide conductivity of 164.4 mS cm(-1) is obtained at a relatively a low ion-exchange capacity of 0.82 mmol g(-1) under optimal operating conditions. The exceptional anion conductivity appears related to the intrinsic microporosity of the charged polymer matrix, which facilitates rapid anion transport. PMID:27505421

  11. Bioinspired porous membranes containing polymer nanoparticles for wound healing.

    PubMed

    Ferreira, Ana M; Mattu, Clara; Ranzato, Elia; Ciardelli, Gianluca

    2014-12-01

    Skin damages covering a surface larger than 4 cm(2) require a regenerative strategy based on the use of appropriate wound dressing supports to facilitate the rapid tissue replacement and efficient self-healing of the lost or damaged tissue. In the present work, A novel biomimetic approach is proposed for the design of a therapeutic porous construct made of poly(L-lactic acid) (PLLA) fabricated by thermally induced phase separation (TIPS). Biomimicry of ECM was achieved by immobilization of type I collagen through a two-step plasma treatment for wound healing. Anti-inflammatory (indomethacin)-containing polymeric nanoparticles (nps) were loaded within the porous membranes in order to minimize undesired cell response caused by post-operative inflammation. The biological response to the scaffold was analyzed by using human keratinocytes cell cultures. In this work, a promising biomimetic construct for wound healing and soft tissue regeneration with drug-release properties was fabricated since it shows (i) proper porosity, pore size, and mechanical properties, (ii) biomimicry of ECM, and (iii) therapeutic potential. PMID:24522948

  12. Pt/C-Electrocatalyst Painting on Polymer Electrolyte Membrane by Electrostatic Spray Deposition

    NASA Astrophysics Data System (ADS)

    Umeda, Minoru; Kawaguchi, Syunsuke; Yamada, Akifumi; Uchida, Isamu

    2005-02-01

    An electrocatalyst painting technique for use in a limited surface area of a polymer electrolyte membrane has been developed by employing electrostatic spray deposition (ESD). ESD is a process in which an aerosol of a solution is ejected from a metal syringe nozzle with a high applied voltage under atmosphere to obtain a thin film on the counter electrode. First, a dispersion containing Pt-loading carbon (Pt/C) powder and Nafion solution was sprayed by using the ESD technique. As a result, the dispersion was deposited over the entire surface area of a polymer electrolyte membrane of Nafion that was placed on the counter Au electrode, whereas, the dispersion was neither deposited on an electric-insulating poly(ethylene telephthalete) (PET) nor on the Nafion membrane on the PET. For the experiment, the Nafion membrane was pretreated to give it ionic conductivity. Next, a dye solution containing Rhodamine B was sprayed in the same manner, with the same result. In the case where the sizes of Nafion membrane and Au electrode were the same, the deposition only occurred on the Nafion/Au layered structure. According to these results, the aerosol generated at the syringe nozzle is introduced to the conductive area and kept away from the insulating area. Finally, for the untreated Nafion membrane on which a water droplet was placed, ESD of the Pt/C dispersion was conducted. Consequently, an electrocatalyst layer was successfully formed only at the wetted point of the Nafion membrane. This technique enables the painting of an electrocatalyst layer over a limited area without the use of any surface mask.

  13. Aqueous Phase Synthesis of ZIF-8 Membrane with Controllable Location on an Asymmetrically Porous Polymer Substrate.

    PubMed

    Shamsaei, Ezzatollah; Lin, Xiaocheng; Low, Ze-Xian; Abbasi, Zahra; Hu, Yaoxin; Liu, Jefferson Zhe; Wang, Huanting

    2016-03-01

    In this study, we have demonstrated a simple, scalable, and environmentally friendly route for controllable fabrication of continuous, well-intergrown ZIF-8 on a flexible polymer substrate via contra-diffusion method in conjunction with chemical vapor modification of the polymer surface. The combined chemical vapor modification and contra-diffusion method resulted in controlled formation of a thin, defect-free, and robust ZIF-8 layer on one side of the support in aqueous solution at room temperature. The ZIF-8 membrane exhibited propylene permeance of 1.50 × 10(-8) mol m(-2) s(-1) Pa(-1) and excellent selective permeation properties; after post heat-treatment, the membrane showed ideal selectivities of C3H6/C3H8 and H2/C3H8 as high as 27.8 and 2259, respectively. The new synthesis approach holds promise for further development of the fabrication of high-quality polymer-supported ZIF membranes for practical separation applications. PMID:26886288

  14. Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells.

    PubMed

    Proietti, Eric; Jaouen, Frédéric; Lefèvre, Michel; Larouche, Nicholas; Tian, Juan; Herranz, Juan; Dodelet, Jean-Pol

    2011-01-01

    H(2)-air polymer-electrolyte-membrane fuel cells are electrochemical power generators with potential vehicle propulsion applications. To help reduce their cost and encourage widespread use, research has focused on replacing the expensive Pt-based electrocatalysts in polymer-electrolyte-membrane fuel cells with a lower-cost alternative. Fe-based cathode catalysts are promising contenders, but their power density has been low compared with Pt-based cathodes, largely due to poor mass-transport properties. Here we report an iron-acetate/phenanthroline/zeolitic-imidazolate-framework-derived electrocatalyst with increased volumetric activity and enhanced mass-transport properties. The zeolitic-imidazolate-framework serves as a microporous host for phenanthroline and ferrous acetate to form a catalyst precursor that is subsequently heat treated. A cathode made with the best electrocatalyst from this work, tested in H(2)-O(2,) has a power density of 0.75 W cm(-2) at 0.6 V, a meaningful voltage for polymer-electrolyte-membrane fuel cells operation, comparable with that of a commercial Pt-based cathode tested under identical conditions. PMID:21811245

  15. Solidification Behavior of Polymer Solution during Membrane Preparation by Thermally Induced Phase Separation

    PubMed Central

    Ishigami, Toru; Nii, Yoko; Ohmukai, Yoshikage; Rajabzadeh, Saeid; Matsuyama, Hideto

    2014-01-01

    The solidification behavior of poly(vinylidene fluoride) (PVDF) solution during membrane preparation by thermally induced phase separation (TIPS) was investigated. Apparatus newly developed in our laboratory was used to quantitatively measure membrane stiffness during phase separation. In this apparatus, a cooling polymer solution, placed on a stage, is moved upwards and the surface of the polymer solution contacts a sphere attached to the tip of a needle. The displacement of a blade spring attached to the needle is then measured by a laser displacement sensor. Different phase separation modes, such as liquid-liquid (L-L) phase separation and solid-liquid (S-L) phase separation (polymer crystallization) were investigated. In the case of S-L phase separation, the stiffness of the solution surface began to increase significantly just before termination of crystallization. In contrast, L-L phase separation delayed solidification of the solution. This was because mutual contact of the spherulites was obstructed by droplets of polymer-lean phase formed during L-L phase separation. Thus, the solidification rate was slower for the L-L phase separation system than for the S-L phase separation system. PMID:24957124

  16. Membrane filtration: An unconventional route for fabrication of the flexible and dissolvable, polymer microneedle patches.

    PubMed

    Juang, Yi-Je; Deng, Yu-Luen; Lee, I-Chi

    2016-07-01

    Utilization of dissolvable, polymer microneedles (MNs) for transdermal drug delivery offers many advantages such as being painless to patients, biocompatibility, biodegradability, and active and controlled drug release. There are many different approaches for fabrication of such MNs; however, most of them still suffer from tedious procedures, stringent fabrication conditions, expensive equipment, or substantially long processing time. In this work, we applied membrane filtration to fabricate dissolvable, polymer MNs. The polydimethylsiloxane mold having pyramidal wells with through holes was constructed and placed on top a filter membrane. The polymer solution was then dispensed on top of the mold, followed by turning on the vacuum for filtration. It was found that, when using 22% polyvinylpyrrolidone (PVP) solution with molecular weight of 360 000 g/mol, the PVP MNs were obtained within 1 h, which is relatively short time compared to the conventional methods like casting in conjunction with vacuum or centrifugation. Moreover, the MNs as fabricated possessed the similar mechanical strength compared to those by conventional methods and were able to penetrate the rat ear skin with a high insertion ratio. The proposed technique provides an attractive alternative to fabricate dissolvable and flexible, polymer MNs with a simple setup and easy procedures. PMID:27570573

  17. Development and properties of the {open_quotes}Stonehart{close_quotes} humidity stabilized perfluoro-polymer membrane

    SciTech Connect

    Stonehart, P.

    1996-12-31

    The purpose of this paper is to examine the role that water plays in the Polymer (or Proton) Electrolyte Membrane Fuel Cells (PEMFCs -- also called PEFCs). Since proton conduction is the main ionic charge carrier, it is worthwhile to examine how this happens and how the water interacts with the perfluoro-polymer structures; examining the microstructure of the membranes and how they have been modified to overcome the water transport limitations inherent in the PEMFC.

  18. Fabrication of zeolite/polymer multilayer composite membranes for carbon dioxide capture: Deposition of zeolite particles on polymer supports.

    PubMed

    Ramasubramanian, Kartik; Severance, Michael A; Dutta, Prabir K; Ho, W S Winston

    2015-08-15

    Membranes, due to their smaller footprint and potentially lower energy consumption than the amine process, offer a promising route for post-combustion CO2 capture. Zeolite Y based inorganic selective layers offer a favorable combination of CO2 permeance and CO2/N2 selectivity, membrane properties crucial to the economics. For economic viability on large scale, we propose to use flexible and scalable polymer supports for inorganic selective layers. The work described in this paper developed a detailed protocol for depositing thin zeolite Y seed layers on polymer supports, the first step in the synthesis of a polycrystalline zeolite Y membrane. We also studied the effects of support surface morphology (pore size and surface porosity) on the quality of deposition and identified favorable supports for the deposition. Two different zeolite Y particles with nominal sizes of 200 nm and 40 nm were investigated. To obtain a complete coverage of zeolite particles on the support surface with minimum defects and in a reproducible manner, a vacuum-assisted dip-coating technique was developed. Images obtained using both digital camera and optical microscope showed the presence of color patterns on the deposited surface which suggested that the coverage was complete. Electron microscopy revealed that the particle packing was dense with some drying cracks. Layer thickness with the larger zeolite Y particles was close to 1 μm while that with the smaller particles was reduced to less than 0.5 μm. In order to reduce drying cracks for layers with smaller zeolite Y particles, thickness was reduced by lowering the dispersion concentration. Transport measurement was used as an additional technique to characterize these layers. PMID:25950846

  19. Generic Role of Polymer Supports in the Fine Adjustment of Interfacial Interactions between Solid Substrates and Model Cell Membranes.

    PubMed

    Rossetti, Fernanda F; Schneck, Emanuel; Fragneto, Giovanna; Konovalov, Oleg V; Tanaka, Motomu

    2015-04-21

    To understand the generic role of soft, hydrated biopolymers in adjusting interfacial interactions at biological interfaces, we designed a defined model of the cell-extracellular matrix contacts based on planar lipid membranes deposited on polymer supports (polymer-supported membranes). Highly uniform polymer supports made out of regenerated cellulose allow for the control of film thickness without changing the surface roughness and without osmotic dehydration. The complementary combination of specular neutron reflectivity and high-energy specular X-ray reflectivity yields the equilibrium membrane-substrate distances, which can quantitatively be modeled by computing the interplay of van der Waals interaction, hydration repulsion, and repulsion caused by the thermal undulation of membranes. The obtained results help to understand the role of a biopolymer in the interfacial interactions of cell membranes from a physical point of view and also open a large potential to generally bridge soft, biological matter and hard inorganic materials. PMID:25794040

  20. Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Membrane structure and transport properties

    SciTech Connect

    Sodeye, Akinbode; Huang, Tianzi; Gido, Samuel; Mays, Jimmy

    2011-01-01

    With a view to optimizing morphology and ultimately properties, membranes have been cast from relatively inexpensive block copolymer ionomers of fluorinated polyisoprene-block-sulfonated polystyrene (FISS) with various sulfonation levels, in both the acid form and the cesium neutralized form. The morphology of these membranes was characterized by transmission electron microscopy and ultra-small angle X-ray scattering, as well as water uptake, proton conductivity and methanol permeability within the temperature range from 20 to 60 C. Random phase separated morphologies were obtained for all samples except the cesium sample with 50 mol% sulfonation. The transport properties increased with increasing degree of sulfonation and temperature for all samples. The acid form samples absorbed more water than the cesium samples with a maximum swelling of 595% recorded at 60 C for the acid sample having 50 mol% sulfonation. Methanol permeability for the latter sample was more than an order of magnitude less than for Nafion 112 but so was the proton conductivity within the plane of the membrane at 20 C. Across the plane of the membrane this sample had half the conductivity of Nafion 112 at 60 C.

  1. The effect of porosity on performance of phosphoric acid doped polybenzimidazole polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Celik, Muhammet; Genc, Gamze; Elden, Gulsah; Yapici, Huseyin

    2016-03-01

    A polybenzimidazole (PBI) based polymer electrolyte fuel cells, which called high temperature polymer electrolyte fuel cells (HT-PEMS), operate at higher temperatures (120-200°C) than conventional PEM fuel cells. Although it is known that HT-PEMS have some of the significant advantages as non-humidification requirements for membrane and the lack of liquid water at high temperature in the fuel cell, the generated water as a result of oxygen reduction reaction causes in the degradation of these systems. The generated water absorbed into membrane side interacts with the hydrophilic PBI matrix and it can cause swelling of membrane, so water transport mechanism in a membrane electrode assembly (MEA) needs to be well understood and water balance must be calculated in MEA. Therefore, the water diffusion transport across the electrolyte should be determined. In this study, various porosity values of gas diffusion layers are considered in order to investigate the effects of porosity on the water management for two phase flow in fuel cell. Two-dimensional fuel cell with interdigitated flow-field is modelled using COMSOL Multiphysics 4.2a software. The operating temperature and doping level is selected as 160°C and 6.75mol H3PO4/PBI, respectively.

  2. Cation-containing Polymers with Co-continuous Microphase-Separated Morphologies for Rapid Transport Membranes

    NASA Astrophysics Data System (ADS)

    Beyer, Frederick; Price, Samuel; Savage, Alice; Ren, Xiaoming; Pomerantz, Natalie; Zukas, Walter

    2015-03-01

    Cation-containing polymer membranes are the subject of renewed research for their potential to enable the use of alkaline fuel cells, and are also of interest for their water vapor transport properties. Charge and water vapor transport are both heavily dependent on membrane morphology and the development of hydrophilic channels throughout the material. Reaction induced phase separation has been shown to create such morphologies when used with uncharged copolymers and crosslinking monomers. Here we have applied this same technique but used ion-containing block copolymers of 4-vinylbenzyltrimethylammonium chloride and styrene to create a cation-containing polymer membrane having a microphase-separated, co-continuous morphology, as characterized by small-angle X-ray scattering (SAXS) and high-angle annular dark field scanning transmission electron microscopy (HAADF STEM). These materials show excellent charge transport behavior and water vapor transport properties, surpassing commercially available materials. These results and efforts to improve other important physical characteristics for membrane applications will be presented.

  3. Research on the Changes to the Lipid/Polymer Membrane Used in the Acidic Bitterness Sensor Caused by Preconditioning.

    PubMed

    Harada, Yuhei; Noda, Junpei; Yatabe, Rui; Ikezaki, Hidekazu; Toko, Kiyoshi

    2016-01-01

    A taste sensor that uses lipid/polymer membranes can evaluate aftertastes felt by humans using Change in membrane Potential caused by Adsorption (CPA) measurements. The sensor membrane for evaluating bitterness, which is caused by acidic bitter substances such as iso-alpha acid contained in beer, needs an immersion process in monosodium glutamate (MSG) solution, called "MSG preconditioning". However, what happens to the lipid/polymer membrane during MSG preconditioning is not clear. Therefore, we carried out three experiments to investigate the changes in the lipid/polymer membrane caused by the MSG preconditioning, i.e., measurements of the taste sensor, measurements of the amount of the bitterness substance adsorbed onto the membrane and measurements of the contact angle of the membrane surface. The CPA values increased as the preconditioning process progressed, and became stable after 3 d of preconditioning. The response potentials to the reference solution showed the same tendency of the CPA value change during the preconditioning period. The contact angle of the lipid/polymer membrane surface decreased after 7 d of MSG preconditioning; in short, the surface of the lipid/polymer membrane became hydrophilic during MSG preconditioning. The amount of adsorbed iso-alpha acid was increased until 5 d preconditioning, and then it decreased. In this study, we revealed that the CPA values increased with the progress of MSG preconditioning in spite of the decrease of the amount of iso-alpha acid adsorbed onto the lipid/polymer membrane, and it was indicated that the CPA values increase because the sensor sensitivity was improved by the MSG preconditioning. PMID:26891299

  4. Research on the Changes to the Lipid/Polymer Membrane Used in the Acidic Bitterness Sensor Caused by Preconditioning

    PubMed Central

    Harada, Yuhei; Noda, Junpei; Yatabe, Rui; Ikezaki, Hidekazu; Toko, Kiyoshi

    2016-01-01

    A taste sensor that uses lipid/polymer membranes can evaluate aftertastes felt by humans using Change in membrane Potential caused by Adsorption (CPA) measurements. The sensor membrane for evaluating bitterness, which is caused by acidic bitter substances such as iso-alpha acid contained in beer, needs an immersion process in monosodium glutamate (MSG) solution, called “MSG preconditioning”. However, what happens to the lipid/polymer membrane during MSG preconditioning is not clear. Therefore, we carried out three experiments to investigate the changes in the lipid/polymer membrane caused by the MSG preconditioning, i.e., measurements of the taste sensor, measurements of the amount of the bitterness substance adsorbed onto the membrane and measurements of the contact angle of the membrane surface. The CPA values increased as the preconditioning process progressed, and became stable after 3 d of preconditioning. The response potentials to the reference solution showed the same tendency of the CPA value change during the preconditioning period. The contact angle of the lipid/polymer membrane surface decreased after 7 d of MSG preconditioning; in short, the surface of the lipid/polymer membrane became hydrophilic during MSG preconditioning. The amount of adsorbed iso-alpha acid was increased until 5 d preconditioning, and then it decreased. In this study, we revealed that the CPA values increased with the progress of MSG preconditioning in spite of the decrease of the amount of iso-alpha acid adsorbed onto the lipid/polymer membrane, and it was indicated that the CPA values increase because the sensor sensitivity was improved by the MSG preconditioning. PMID:26891299

  5. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    DOE PAGESBeta

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for furthermore » development of this new class of solid electrolytes.« less

  6. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    SciTech Connect

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

    A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10-4 S cm-1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to tLi+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting design parameters for further development of this new class of solid electrolytes.

  7. Modeling Methane Adsorption in Interpenetrating Porous Polymer Networks

    SciTech Connect

    Martin, RL; Shahrak, MN; Swisher, JA; Simon, CM; Sculley, JP; Zhou, HC; Smit, B; Haranczyk, M

    2013-10-03

    Porous polymer networks (PPNs) are a class of porous materials of particular interest in a variety of energy-related applications because of their stability, high surface areas, and gas uptake capacities. Computationally derived structures for five recently synthesized PPN frameworks, PPN-2, -3, -4, -5, and -6, were generated for various topologies, optimized using semiempirical electronic structure methods, and evaluated using classical grand canonical Monte Carlo simulations. We show that a key factor in modeling the methane uptake performance of these materials is whether, and how, these material frameworks interpenetrate and demonstrate a computational approach for predicting the presence, degree, and nature of interpenetration in PPNs that enables the reproduction of experimental adsorption data.

  8. Cascade synthesis of a gold nanoparticle-network polymer composite

    NASA Astrophysics Data System (ADS)

    Grubjesic, Simonida; Ringstrand, Bryan S.; Jungjohann, Katherine L.; Brombosz, Scott M.; Seifert, Sönke; Firestone, Millicent A.

    2016-01-01

    The multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical initiated polymerization and crosslinking of the acrylate end-derivatized PEO117-PPO47-PEO117 to yield a network polymer. Optical spectroscopy and TEM monitored the reduction of [AuCl4]-, formation of large aggregated Au NPs and oxidative etching into a final state of dispersed, spherical Au NPs. ATR/FT-IR spectroscopy and thermal analysis confirms acrylate crosslinking to yield the polymer network. X-ray scattering (SAXS and WAXS) monitored the evolution of the multi-lamellar structured mesophase and revealed the presence of semi-crystalline PEO confined within the water layers. The hydrogel could be reversibly swollen without loss of the well-entrained Au NPs with full recovery of composite structure. Optical spectroscopy shows a notable red shift (Δλ ~ 45 nm) in the surface plasmon resonance between swollen and contracted states, demonstrating solvent-mediated modulation of the internal NP packing arrangement.The multi-step, cascade synthesis of a self-supporting, hierarchically-structured gold nanoparticle hydrogel composite is described. The composite is spontaneously prepared from a non-covalent, lamellar lyotropic mesophase composed of amphiphiles that support the reactive constituents, a mixture of hydroxyl- and acrylate-end-derivatized PEO117-PPO47-PEO117 and [AuCl4]-. The reaction sequence begins with the auto-reduction of aqueous [AuCl4]- by PEO117-PPO47-PEO117 which leads to both the production of Au NPs and the free radical

  9. Proton Conducting Polymer Membrane Using The Ionic Liquid 2-Hydroxyethylammonium Lactate For Ethanol Fuel Cells

    NASA Astrophysics Data System (ADS)

    Oliveira, L.; José, N. M.; Boaventura, J.; Iglesias, M.; Mattedi, S.

    2011-12-01

    In this work, there were developed a proton conducting polymer membrane using an ammonium based protic ionic liquid: 2-hydroxyethylamominum lactate for use in proton exchange fuel cells (PEMFC). This kind of ionic liquid has been proven to be biodegradable and they have potentially low toxicity besides low cost of preparation, simple synthesis and purification. The prepared membranes are hybrid organic-inorganic materials. The polymeric matrix is prepared with polydimethylsiloxane (PDMS) mixed with tetraethoxysilane (TEOS) in a ratio of 70/30% in weight. Then, the eletrolytical mixture containing sodium monododecylsulfate (SDS) and the ionic liquid was introduced in the lattice near the gel point, there were used different proportions of the eletrolyte from 5 to 30% in weight. The prepared membranes were characterized using infrared spectroscopy (FTIR), X-ray diffraction (DRX), termogravimetric analysis (TGA), scanning electronic microscopy (SEM) and conductivity and impedance measurements. The prepared materials are flexible, with good thermal and mechanical stability and with a great potential to be used as conducting membranes of fuel cells. The used mixture minimizes the lixiviation lost of the ionic liquid from the polymeric membrane and enhances the cell efficiency if compared with traditional synthetic membranes.

  10. Enhanced ionic polymer metal composite actuator with porous nafion membrane using zinc oxide particulate leaching method

    NASA Astrophysics Data System (ADS)

    Jung, Sun Yong; Ko, Seong Young; Park, Jong-Oh; Park, Sukho

    2015-03-01

    In this study, to improve the performance of an ionic polymer metal composite (IPMC), we suggest a porous nafion membrane fabricated with the particulate leaching method with zinc oxide and propose an IPMC that uses the porous nafion membrane. To fabricate this membrane, the proper ratio of nafion and zinc oxide powder is dispersed in a solvent. Then the zinc oxide embedded in the nafion membrane is fabricated with a casting method. With the particulate leaching method, the embedded zinc oxide particles are dissolved by an acid solution, and the spaces of the zinc oxide particles changed to pores. Finally, through electroless plating and ion exchange procedures, an IPMC with the porous nafion membrane is fabricated. The proposed IPMC has higher water uptake (WUP) and ion exchange capacity (IEC) and can show better actuation performance compared to the conventional nafion-based IPMC. We also measure the actuation displacement and blocking forces of the proposed IPMC. Compared with the conventional nafion-based IPMC, the proposed IPMC with the porous nafion membrane has increased displacements: about 80% at ac input and about 250% at dc input, and increased blocking force about 130% at dc input.

  11. Ordered structures in proton conducting membranes from supramolecular liquid crystal polymers.

    PubMed

    Every, Hayley A; Mendes, Eduardo; Picken, Stephen J

    2006-11-30

    Highly sulfonated forms of poly(p-phenylene terephthalamide) (PPTA) have been prepared in three different molecular configurations; sulfonated diamine form (S-PPTA), sulfonated terephthalic acid form (S-invert-PPTA), and the bi-sulfonated form (S2-PPTA). All three polymers are water soluble to a certain degree and films were cast from solution for S-PPTA and S-invert-PPTA. S-PPTA films absorb less water than S-invert-PPTA (under controlled humidity conditions) and consequently, the conductivity for this polymer is also slightly lower. Although the conductivities are comparable to Nafion (of the order of 10(-2) to 10(-1) Scm(-1)), proton mobility is more restricted. X-ray diffraction showed that the rigid molecules are aligned in opposite directions for the two polymer films, being homeotropic in S-PPTA films and planar for S-invert-PPTA. SEM analysis demonstrated layering in the same direction as the alignment of the polymer chains. The variation in the polymer alignment is most likely the result of the differences in the solution properties and the film forming process. It is possible, however, that this alignment could be exploited to enhance proton transport and thus these films are of interest for fuel cell membranes. PMID:17125333

  12. Lowering the platinum loading of high temperature polymer electrolyte membrane fuel cells with acid doped polybenzimidazole membranes

    NASA Astrophysics Data System (ADS)

    Martin, S.; Li, Q.; Jensen, J. O.

    2015-10-01

    Membrane electrode assemblies (MEAs) with ultra-low Pt loading electrodes were prepared for high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) based on acid doped polybenzimidazole. With no electrode binders or ionomers, the triple phase boundary of the catalyst layer was established by the acid transfer from the acid doped membrane to the electrodes and can therefore be tailored by using catalysts with varied Pt to C ratios. With a loading of ca. 0.1 mgPtcm-2 on each electrode the best performance was obtained with electrodes prepared from 10 wt.% Pt/C due to the improved Pt dispersion, extended triple phase boundary upon the acid transfer and the alleviated acid flooding of the catalytic layer. The MEA delivered a peak power density of 482 mW cm-2 for H2/O2 and 321 mW cm-2 for H2/air, corresponding to an overall Pt utilization of 2.5 and 1.7 kW gPt-1, respectively. The durability test revealed no net voltage decay during more than 1700 h of uninterrupted operation at 200 mA cm-2 and 160 °C.

  13. High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte.

    PubMed

    Kuo, Ping-Lin; Wu, Ching-An; Lu, Chung-Yu; Tsao, Chin-Hao; Hsu, Chun-Han; Hou, Sheng-Shu

    2014-03-12

    A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes. PMID:24521309

  14. The shape memory effect in crosslinked polymers: effects of polymer chemistry and network architecture

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Li, Yali; Goulbourne, N. C.

    2013-04-01

    The thermal shape memory effect in polymeric materials refers to the ability of a sample to retain a deformed shape when cooled below Tg, and then recover its initial shape when subsequently heated. Although these properties are thought to be related to temperature-dependent changes in network structure and polymer chain mobility, a consistent picture of the molecular mechanisms which determine shape memory behavior does not exist. This, along with large differences in the shape memory cycling response for different materials, has made model development and specific property optimization difficult. In this work we use coarse-grained molecular dynamics (MD) simulations of the thermal shape memory effect to inform micro-macro relationships and systematically identify the salient features leading to desirable shape behavior. We consider a simulation test set including chains with increasing levels of the microscopic restrictions on chain motion (the freely-jointed, freely-rotating, and rotational isomeric state chain models), each simulated with both the NPT and NVT ensembles. It is found that the NPT ensemble with attractive interactions between monomers enabled is the most appropriate for simulating the temperature-dependent mechanical behavior of a polymer using coarse-grained MD. Of the different models, the freely-jointed chain system shows the most desirable shape memory characteristics; this behavior is attributed to the ability of the particles in this system to pack closely together in an energetically favorable configuration. A comparison with experimental data demonstrates that the coarse-grained simulations display all of the relevant trends in mechanical behavior during constant strain shape memory cycling. We conclude that atomistic detail is not needed to represent a shape memory polymer, and that multi-scale modeling techniques may build on the mechanisms embodied in the simple coarse-grained model.

  15. Investigation of Cross-Linked and Additive Containing Polymer Materials for Membranes with Improved Performance in Pervaporation and Gas Separation

    PubMed Central

    Hunger, Katharina; Schmeling, Nadine; Jeazet, Harold B. Tanh; Janiak, Christoph; Staudt, Claudia; Kleinermanns, Karl

    2012-01-01

    Pervaporation and gas separation performances of polymer membranes can be improved by crosslinking or addition of metal-organic frameworks (MOFs). Crosslinked copolyimide membranes show higher plasticization resistance and no significant loss in selectivity compared to non-crosslinked membranes when exposed to mixtures of CO2/CH4 or toluene/cyclohexane. Covalently crosslinked membranes reveal better separation performances than ionically crosslinked systems. Covalent interlacing with 3-hydroxypropyldimethylmaleimide as photocrosslinker can be investigated in situ in solution as well as in films, using transient UV/Vis and FTIR spectroscopy. The photocrosslinking yield can be determined from the FTIR-spectra. It is restricted by the stiffness of the copolyimide backbone, which inhibits the photoreaction due to spatial separation of the crosslinker side chains. Mixed-matrix membranes (MMMs) with MOFs as additives (fillers) have increased permeabilities and often also selectivities compared to the pure polymer. Incorporation of MOFs into polysulfone and Matrimid® polymers for MMMs gives defect-free membranes with performances similar to the best polymer membranes for gas mixtures, such as O2/N2 H2/CH4, CO2/CH4, H2/CO2, CH4/N2 and CO2/N2 (preferentially permeating gas is named first). The MOF porosity, its particle size and content in the MMM are factors to influence the permeability and the separation performance of the membranes. PMID:24958427

  16. Selective, ultrathin membrane skins prepared by deposition of novel polymer films on porous alumina supports

    NASA Astrophysics Data System (ADS)

    Balachandra, Anagi Manjula

    Membrane-based separations are attractive in industrial processes because of their low energy costs and simple operation. However, low permeabilities often make membrane processes uneconomical. Since flux is inversely proportional to membrane thickness, composite membranes consisting of ultrathin, selective skins on highly permeable supports are required to simultaneously achieve high throughput and high selectivity. However, the synthesis of defect-free skins with thicknesses less than 50 nm is difficult, and thus flux is often limited. Layer-by-layer deposition of oppositely charged polyelectrolytes on porous supports is an attractive method to synthesize ultrathin ion-separation membranes with high flux and high selectivity. The ion-transport selectivity of multilayer polyelectrolyte membranes (MPMs) is primarily due to Donnan exclusion; therefore increase in fixed charge density should yield high selectivity. However, control over charge density in MPMs is difficult because charges on polycations are electrostatically compensated by charges on polyanions, and the net charge in the bulk of these films is small. To overcome this problem, we introduced a templating method to create ion-exchange sites in the bulk of the membrane. This strategy involves alternating deposition of a Cu2+-poly(acrylic acid) complex and poly(allylamine hydrochloride) on a porous alumina support followed by removal of Cu2+ and deprotonation to yield free -COO- ion-exchange sites. Diffusion dialysis studies showed that the Cl-/SO42-. Selectivity of Cu2+-templated membranes is 4-fold higher than that of membranes prepared in the absence of Cu2+. Post-deposition cross-linking of these membranes by heat-induced amide bond formation further increased Cl-/SO42- selectivity to values as high as 600. Room-temperature, surface-initiated atom transfer radical polymerization (ATRP) provides another convenient method for formation of ultrathin polymer skins. This process involves attachment of

  17. Structural Properties and Phase Behavior of Crosslinked Networks in Polymer Solutions

    PubMed Central

    Benmouna, Farida; Zemmour, Samira; Benmouna, Mustapha

    2016-01-01

    ABSTRACT Structural properties and phase behavior of crosslinked networks embedded in polymer solutions are theoretically investigated. The partial structure factor of the network is calculated using a matrix formulation of the random phase approximation and the forward scattering limit is correlated with the phase behavior. Swelling and deswelling processes are analyzed in terms of the polymer concentration, the mismatch of solvent quality with respect to polymer and network, the polymers incompatibility and their characteristic sizes. Most studies reported so far in the literature have focussed on the swelling of crosslinked networks and gels in pure solvents but the correlation of the structural properties with the phase behavior in the presence of high molecular weight polymers in solution has not been given sufficient attention. The present work is intended to fill this gap in view of the current efforts to develop novel drug encapsulating and targeted delivery devices. PMID:27134310

  18. Picosecond fiber laser microfabrication of THz wire-grid polarizers on polymer membrane substrates

    NASA Astrophysics Data System (ADS)

    Gerke, Tim D.; Fast, Dylan; Kozlov, Vladimir G.

    2012-03-01

    Ultrafast picosecond lasers provide the gentle cold ablation required to selectively remove a 400 nm metal film from an unsupported ultra-thin polymer membrane without damaging the membrane substrate. Selected areas of the metal film are completely removed in an ablative lift-off process enabled by a single laser pulse. No damage to the polymer membrane is observed even for samples with the metal completely removed over a 50x50 mm area of the membrane. The 400 nm thick metal films can be patterned into arbitrary forms with feature sizes as small as 10 micrometers, and even submicron features are realistically possible with a modification to the processing system. The skin depth of aluminium in the THz regime is significantly shorter than the 400 nm metal thickness, so thicker metal films that are significantly more difficult to machine are not beneficial. As an example, thin-film wire grid polarizers for the THz regime are demonstrated. The thin-film polarizers are much easier and faster to fabricate than polarizers made by winding free-standing wires around a frame and their performance is very comparable. The thin-film polarizers also have the added benefit of a significantly higher potential for functionality deeper in to the THz spectrum due to their capacity for smaller feature sizes. More intricate patterns, such as meshes, can also be made to create THz bandpass filters. This method can be extended to cold ablation processing of multilayer films fabricated on thin polymer substrates for applications such as plastic electronics, displays and solar cells.

  19. Mean-square displacement of particles in slightly interconnected polymer networks.

    PubMed

    Sarmiento-Gomez, Erick; Santamaría-Holek, Iván; Castillo, Rolando

    2014-01-30

    Structural and viscoelastic properties of slightly interconnected polymer networks immersed in a solvent have been studied in two cases: when the polymer network is building up and when the polymer network is shrinking stepwise in a controlled way. To accomplish this goal, the mean square displacement (MSD) of embedded microspheres in the polymer network was measured as a function of time, with diffusive wave spectroscopy. Particle motion was analyzed in terms of a model, based on a Fokker-Planck type equation, developed for describing particles in Brownian motion within a network that constrain their movement. The model reproduces well the experimental features observed in the MSD vs t curves. The variation of the parameters describing the structure of the network can be understood as the polymerization comes about, and also after the successive volume contractions. In addition, from the MSD curves, the complex shear moduli were obtained in a wide range of frequencies when the network is building up, and at the different shrinking states of the network. Our microrheological results give an insight about the dynamics of embedded particles in slightly interconnected networks, which were also compared with similar results for polymers without interconnections and polymer gels. PMID:24423025

  20. Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

    SciTech Connect

    Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

    2015-02-24

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

  1. Surfactant self-assembly in oppositely charged polymer networks. Theory.

    PubMed

    Hansson, Per

    2009-10-01

    The interaction of ionic surfactants with polyion networks of opposite charge in an aqueous environment is analyzed theoretically by applying a recent theory of surfactant ion-polyion complex salts (J. Colloid. Int. Sci. 2009, 332, 183). The theory takes into account attractive and repulsive polyion-mediated interactions between the micelles, the deformation of the polymer network, the mixing of micelles, polyion chains, and simple ions with water, and the hydrophobic free energy at the micelle surface. The theory is used to calculate binding isotherms, swelling isotherms, surfactant aggregation numbers, compositions of complexes,and phase structure under various conditions. Factors controlling the gel volume transition and conditions for core/shell phase coexistence are investigated in detail, as well as the influence of salt. In particular, the interplay between electrostatic and elastic interactions is highlighted. Results from theory are compared with experimental data reported in the literature. The agreement is found to be semiquantitative or qualitative. The theory explains both the discrete volume transition observed in systems where the surfactant is in excess over the polyion and the core/shell phase coexistence in systems where the polyion is in excess. PMID:19728696

  2. Functionalized carbon nanotubes mixed matrix membranes of polymers of intrinsic microporosity for gas separation

    PubMed Central

    2012-01-01

    The present work reports on the gas transport behavior of mixed matrix membranes (MMM) which were prepared from multi-walled carbon nanotubes (MWCNTs) and dispersed within polymers of intrinsic microporosity (PIM-1) matrix. The MWCNTs were chemically functionalized with poly(ethylene glycol) (PEG) for a better dispersion in the polymer matrix. MMM-incorporating functionalized MWCNTs (f-MWCNTs) were fabricated by dip-coating method using microporous polyacrylonitrile membrane as a support and were characterized for gas separation performance. Gas permeation measurements show that MMM incorporated with pristine or functionalized MWCNTs exhibited improved gas separation performance compared to pure PIM-1. The f-MWCNTs MMM show better performance in terms of permeance and selectivity in comparison to pristine MWCNTs. The gas permeances of the derived MMM are increased to approximately 50% without sacrificing the selectivity at 2 wt.% of f-MWCNTs' loading. The PEG groups on the MWCNTs have strong interaction with CO2 which increases the solubility of polar gas and limit the solubility of nonpolar gas, which is advantageous for CO2/N2 selectivity. The addition of f-MWCNTs inside the polymer matrix also improved the long-term gas transport stability of MMM in comparison with PIM-1. The high permeance, selectivity, and long term stability of the fabricated MMM suggest that the reported approach can be utilized in practical gas separation technology. PMID:22953751

  3. The use of radiation-induced graft polymerization for modification of polymer track membranes

    NASA Astrophysics Data System (ADS)

    Shtanko, N. I.; Kabanov, V. Ya.; Apel, P. Yu.; Yoshida, M.

    1999-05-01

    Track membranes (TM) made of poly(ethylene terephtalate) (PET) and polypropylene (PP) films have a number of peculiarities as compared with other ones. They have high mechanical strength at a low thickness, narrow pore size distribution, low content of extractables. However, TM have some disadvantages such as low chemical resistance in alkaline media (PET TM), the low water flow rate due to the hydrophobic nature of their surface. The use of radiation-induced graft polymerization makes it possible to improve the basic characteristics of TM. In this communication our results on the modification of PET and PP TM are presented. The modified membranes were prepared by radiation-induced graft polymerization from the liquid phase. Three methods of grafting were used: (a) the direct method in argon atmosphere; (b) the pre-irradiation of TM in air followed by grafting in argon atmosphere; (c) pre-irradiation in vacuum followed by grafting in vacuum without contacting oxygen. The aim of the work was to investigate some properties of TM modified by grafted poly(methylvinyl pyridine) (PMVP) and poly(N-isopropylacrylamide) (PNIPAAM). It was shown that the modification of TM with hydrophilic polymer results in the growth of the water flow rate. In the past few years many works have been devoted to the synthesis of new polymers - the so-called "intelligent" materials - such as PNIPAAM. However, it is very difficult to make thin membranes of this polymer. Recently, it has been proposed to manufacture composite membranes by grafting stimulus-responsive polymers onto TM. Following this principle, we prepared thermosensitive membranes by the radiation-induced graft polymerization of N-isopropylacrylamide (NIPAAM) onto PET TM. PET TM with the pore size of about 1 μm and pore density of 10 6 cm -2 were first inserted into a solution of NIPAAM containing inhibitor of homopolymerization (CuCl 2) and then exposed to the γ-rays from a 60Co source. The transport properties of the grafted

  4. Structure and membrane remodeling activity of ESCRT-III helical polymers

    DOE PAGESBeta

    McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; Skowyra, Michael L.; Saunders, Marissa G.; Naismith, Teresa V.; Colf, Leremy A.; Afonine, Pavel; Arthur, Christopher; Sundquist, Wesley I.; et al

    2015-12-18

    The endosomal sorting complexes required for transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure, and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 angstrom resolution cryogenic electron microscopy reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, charged multivesicular body protein 1B (CHMP1B) and increased sodium tolerance 1 (IST1). The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecturemore » and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively curved membranes in vitro and in vivo. In conclusion, our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature.« less

  5. Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution.

    PubMed

    Mohapatra, P K; Lakshmi, D S; Bhattacharyya, A; Manchanda, V K

    2009-09-30

    Transport behaviour of (137)Cs from nitric acid feed was investigated using cellulose triacetate plasticized polymer inclusion membrane (PIM) containing several crown ether carriers viz. di-benzo-18-crown-6 (DB18C6), di-benzo-21-crown-7 (DB21C7) and di-tert-butylbenzo-18-crown-6 (DTBB18C6). The PIM was prepared from cellulose triacetate (CTA) with various crown ethers and plasticizers. DTBB18C6 and tri-n-butyl phosphate (TBP) were found to give higher transport rate for (137)Cs as compared to other carriers and plasticizers. Effect of crown ether concentration, nitric acid concentration, plasticizer and CTA concentration on the transport rate of Cs was also studied. The Cs selectivity with respect to various fission products obtained from an irradiated natural uranium target was found to be heavily dependent on the nature of the plasticizer. The present work shows that by choosing a proper plasticizer, one can get either good transport efficiency or selectivity. Though TBP plasticized membranes showed good transport efficiency, it displayed poor selectivities. On the other hand, an entirely opposite separation behaviour was observed with 2-nitrophenyloctylether (NPOE) plasticized membranes suggesting the possible application of the later membranes for the removal of bulk (137)Cs from the nuclear waste. The stability of the membrane was tested by carrying out transport runs for nearly 25 days. PMID:19398153

  6. Structure and membrane remodeling activity of ESCRT-III helical polymers

    SciTech Connect

    McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; Skowyra, Michael L.; Saunders, Marissa G.; Naismith, Teresa V.; Colf, Leremy A.; Afonine, Pavel; Arthur, Christopher; Sundquist, Wesley I.; Hanson, Phyllis I.; Frost, Adam

    2015-12-18

    The endosomal sorting complexes required for transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure, and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 angstrom resolution cryogenic electron microscopy reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, charged multivesicular body protein 1B (CHMP1B) and increased sodium tolerance 1 (IST1). The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecture and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively curved membranes in vitro and in vivo. In conclusion, our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature.

  7. The novel approach to Cd(II) extraction by polymer inclusion membrane using TIOA as carrier

    NASA Astrophysics Data System (ADS)

    Polat, Cüneyt; Eyüpoǧlu, Volkan; Sara, Osman Nuri

    2016-04-01

    In the present study, the novel approach for the extraction of Cd(II) from acidic iodide solutions was achieved by using PVC based polymer inclusion membrane (PIM) technique containing triisooctyl amine (TIOA) as a carrier. PIMs were prepared according to the literature (1) and characterized by in aspects of thickness and surface morphology and molecular characterization. PIM composition was varied to find optimum membrane formation on Cd(II) transport. The effective parameters like thickness, plasticizer type and rate and carrier rate were investigated. Also, as a useful parameter, the concentration in the feed phase was examined to assess the effect on optimized membrane compositions. It was found that the concentration was the most useful parameter in the aqueous phase of Cd(II) transport because the remained I- in the aqueous feed phase unreacted with Cd(II). We recognize that by the time free I- concentration in the feed, the accumulation of the membrane increases and loading capacity of the membrane with CdI42- decreases because of the limited amount of carrier molecules in the PIM. As a result, it is concluded that extraction and separation of Cd(II) from simulated Ni/Cd leach solutions was carried out with higher initial mass transfer and permeation coefficients as 9,07×10-7 mol/m2s and 1,02×10-5 m/s at the optimum conditions respectively.

  8. Linear coupling of alignment with transport in a polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    Li, Jing; Park, Jong Keun; Moore, Robert B.; Madsen, Louis A.

    2011-07-01

    Polymer electrolyte membranes (PEMs) selectively transport ions and polar molecules in a robust yet formable solid support. Tailored PEMs allow for devices such as solid-state batteries,‘artificial muscle’ actuators and reverse-osmosis water purifiers. Understanding how PEM structure and morphology relate to mobile species transport presents a challenge for designing next-generation materials. Material length scales from subnanometre to 1 μm (refs , ) influence bulk properties such as ion conductivity and water transport. Here we employ multi-axis pulsed-field-gradient NMR (ref. ) to measure diffusion anisotropy, and 2H NMR spectroscopy and synchrotron small-angle X-ray scattering to probe orientational order as a function of water content and of membrane stretching. Strikingly, transport anisotropy linearly depends on the degree of alignment, signifying that membrane stretching affects neither the nanometre-scale channel dimensions nor the defect structure,causing only domain reorientation. The observed reorientation of anisotropic domains without perturbation of the inherent nematic-like domain character parallels the behaviour of nematic elastomers, promises tailored membrane conduction and potentially allows understanding of tunable shape-memory effects in PEM materials. This quantitative understanding will drive PEM design efforts towardsoptimal membrane transport, thus enabling more efficient polymeric batteries, fuel cells, mechanical actuators and water purification.

  9. Structure and membrane remodeling activity of ESCRT-III helical polymers

    PubMed Central

    McCullough, John; Clippinger, Amy K.; Talledge, Nathaniel; Skowyra, Michael L.; Saunders, Marissa G.; Naismith, Teresa V.; Colf, Leremy A.; Afonine, Pavel; Arthur, Christopher; Sundquist, Wesley I.; Hanson, Phyllis I.; Frost, Adam

    2015-01-01

    The Endosomal Sorting Complexes Required for Transport (ESCRT) proteins mediate fundamental membrane remodeling events that require stabilizing negative membrane curvature. These include endosomal intralumenal vesicle formation, HIV budding, nuclear envelope closure and cytokinetic abscission. ESCRT-III subunits perform key roles in these processes by changing conformation and polymerizing into membrane-remodeling filaments. Here, we report the 4 Å resolution cryo-EM reconstruction of a one-start, double-stranded helical copolymer composed of two different human ESCRT-III subunits, CHMP1B and IST1. The inner strand comprises “open” CHMP1B subunits that interlock in an elaborate domain-swapped architecture, and is encircled by an outer strand of “closed” IST1 subunits. Unlike other ESCRT-III proteins, CHMP1B and IST1 polymers form external coats on positively-curved membranes in vitro and in vivo. Our analysis suggests how common ESCRT-III filament architectures could stabilize different degrees and directions of membrane curvature. PMID:26634441

  10. Novel Perfluorinated Polymer-Based Pervaporation Membranes for Separation of Solvent/Water Mixtures

    PubMed Central

    Smuleac, V.; Wu, J.; Nemser, S.; Majumdar, S.; Bhattacharyya, D.

    2012-01-01

    Traditionally, the pervaporation of water-solvent mixtures where the solvent is the major component is performed using hydrophilic membranes (such as PVA or zeolites). In the present paper a new type of pervaporation membrane (amorphous perfluorinated polymer, hydrophobic) was studied for separation of water-solvent mixtures. This membrane has high free volume and is inert for all solvents, and has a remarkable mechanical, chemical and thermal stability. The water is transported by solution diffusion model and the separation of solvent is primarily based on molecular sieving (size exclusion) principles. The membrane shows a high stability for operation over a broad range of feed concentrations without swelling; the operating temperature does not have a significant effect on membrane separation performance. Separation factors as high as 349 and 500 for water-ethanol and water-IPA mixtures (2-98 % wt water-solvent) and fluxes of 0.15 and 0.05 kg/m2h, respectively were obtained at 22 °C. The permeance-based selectivities were also calculated, and the selectivity is approximately constant for a wide range of feed concentrations. The pervaporation of more complex (ternary) mixtures of water-ethanol-ethyl acetate showed that this system could be successfully applied for solute separation based on size exclusion. PMID:22879688

  11. Ammonium across a Selective Polymer Inclusion Membrane: Characterization, Transport, and Selectivity.

    PubMed

    Casadellà, Anna; Schaetzle, Olivier; Loos, Katja

    2016-05-01

    The recovery of ammonium from urine requires distinguishing and excluding sodium and potassium. A polymer inclusion membrane selective for ammonium is developed using an ionophore based on pyrazole substituted benzene. The interactions of the components are studied, as well as their effect on transport and selectivity. Spectroscopic and thermogravimetric measurements show no extensive physical interactions of the components, and that the plasticizer reduces the intermolecular forces (rigidity) of the membrane. The ionophore turns the membrane more rigid, although it increases its swelling degree and therefore the affinity of cations. A ratio of plasticizer (DEHP) and polymer (PVC) of 1:3 in mass gives the highest ammonium flux. Tested contents of ionophore (2 and 5 wt%) show that the higher the content of the ionophore, the fastest the flux is (7.5 × 10(-3) mmol cm(-2) h(-1) ). Selectivity of NH4 (+) over Na(+) and over K(+) is reduced from 13.07 to 9.33 and from 14.15 to 9.57 correspondingly. PMID:27062504

  12. Miniaturizable Ion-Selective Arrays Based on Highly Stable Polymer Membranes for Biomedical Applications

    PubMed Central

    Mir, Mònica; Lugo, Roberto; Tahirbegi, Islam Bogachan; Samitier, Josep

    2014-01-01

    Poly(vinylchloride) (PVC) is the most common polymer matrix used in the fabrication of ion-selective electrodes (ISEs). However, the surfaces of PVC-based sensors have been reported to show membrane instability. In an attempt to overcome this limitation, here we developed two alternative methods for the preparation of highly stable and robust ion-selective sensors. These platforms are based on the selective electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT), where the sulfur atoms contained in the polymer covalently interact with the gold electrode, also permitting controlled selective attachment on a miniaturized electrode in an array format. This platform sensor was improved with the crosslinking of the membrane compounds with poly(ethyleneglycol) diglycidyl ether (PEG), thus also increasing the biocompatibility of the sensor. The resulting ISE membranes showed faster signal stabilization of the sensor response compared with that of the PVC matrix and also better reproducibility and stability, thus making these platforms highly suitable candidates for the manufacture of robust implantable sensors. PMID:24999717

  13. Miniaturizable ion-selective arrays based on highly stable polymer membranes for biomedical applications.

    PubMed

    Mir, Mònica; Lugo, Roberto; Tahirbegi, Islam Bogachan; Samitier, Josep

    2014-01-01

    Poly(vinylchloride) (PVC) is the most common polymer matrix used in the fabrication of ion-selective electrodes (ISEs). However, the surfaces of PVC-based sensors have been reported to show membrane instability. In an attempt to overcome this limitation, here we developed two alternative methods for the preparation of highly stable and robust ion-selective sensors. These platforms are based on the selective electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT), where the sulfur atoms contained in the polymer covalently interact with the gold electrode, also permitting controlled selective attachment on a miniaturized electrode in an array format. This platform sensor was improved with the crosslinking of the membrane compounds with poly(ethyleneglycol) diglycidyl ether (PEG), thus also increasing the biocompatibility of the sensor. The resulting ISE membranes showed faster signal stabilization of the sensor response compared with that of the PVC matrix and also better reproducibility and stability, thus making these platforms highly suitable candidates for the manufacture of robust implantable sensors. PMID:24999717

  14. Development of a portable taste sensor with a lipid/polymer membrane.

    PubMed

    Tahara, Yusuke; Nakashi, Kenichi; Ji, Ke; Ikeda, Akihiro; Toko, Kiyoshi

    2013-01-01

    We have developed a new portable taste sensor with a lipid/polymer membrane and conducted experiments to evaluate the sensor's performance. The fabricated sensor consists of a taste sensor chip (40 mm × 26 mm × 2.2 mm) with working and reference electrodes and a portable sensor device (80 mm × 25 mm × 20 mm). The working electrode consists of a taste-sensing site comprising a poly(hydroxyethyl)methacrylate (pHEMA) hydrogel layer with KCl as the electrolyte layer and a lipid/polymer membrane as the taste sensing element. The reference electrode comprises a polyvinyl chloride (PVC) membrane layer with a small hole and a pHEMA layer with KCl. The whole device is the size of a USB memory stick, making it suitable for portable use. The sensor's response to tannic acid as the standard astringency substance showed good accuracy and reproducibility, and was comparable with the performance of a commercially available taste sensing system. Thus, it is possible for this sensor to be used for in-field evaluations and it can make a significant contribution to the food industry, as well as in various fields of research. PMID:23325168

  15. Polymer network/carbon layer on monolith support and monolith catalytic reactor

    DOEpatents

    Nordquist, Andrew Francis; Wilhelm, Frederick Carl; Waller, Francis Joseph; Machado, Reinaldo Mario

    2003-08-26

    The present invention relates to an improved monolith catalytic reactor and a monolith support. The improvement in the support resides in a polymer network/carbon coating applied to the surface of a porous substrate and a catalytic metal, preferably a transition metal catalyst applied to the surface of the polymer network/carbon coating. The monolith support has from 100 to 800 cells per square inch and a polymer network/carbon coating with surface area of from 0.1 to 15 m.sup.2 /gram as measured by adsorption of N.sub.2 or Kr using the BET method.

  16. From ribbons to networks: hierarchical organization of DNA-grafted supramolecular polymers.

    PubMed

    Vyborna, Yuliia; Vybornyi, Mykhailo; Häner, Robert

    2015-11-11

    DNA-grafted supramolecular polymers (SPs) allow the programmed organization of DNA in a highly regular, one-dimensional array. Oligonucleotides are arranged along the edges of pyrene-based helical polymers. Addition of complementary oligonucleotides triggers the assembly of individual nanoribbons resulting in the development of extended supramolecular networks. Network formation is enabled by cooperative coaxial stacking interactions of terminal GC base pairs. The process is accompanied by structural changes in the pyrene polymer core that can be followed spectroscopically. Network formation is reversible, and disassembly into individual ribbons is realized either via thermal denaturation or by addition of a DNA separator strand. PMID:26491956

  17. From polymer chemistry to membrane elaboration. A global approach of fuel cell polymeric electrolytes

    NASA Astrophysics Data System (ADS)

    Iojoiu, C.; Chabert, F.; Maréchal, M.; Kissi, N. El.; Guindet, J.; Sanchez, J.-Y.

    The paper tries to make a critical inventory of Ionomers, free of fluorine or fluorine less, which can be used as alternatives to Nafion ® in polymer electrolytes fuel cells, as Ionomer is indisputably one of the main bolts of these technologies. All the Ionomer families are discussed, with their main advantages and drawbacks, in particular in terms of their possible industrial scale-up. Special attention has been paid to the discussions about the choice of the ionic functions and that of polymeric backbones of the Ionomers, with regard to the required electrochemical properties and also to their thermomechanical behaviour. It has been emphasized that a global approach of the polymer electrolytes is essential to progress. This must involve (i) a control of the syntheses up to the pilot scale, (ii) thorough characterizations, (iii) attention to the membrane and the MEA assembly and (iv) durability investigations, including post-mortem characterizations.

  18. Photophysics of Laser Dye-Doped Polymer Membranes for Laser-Induced Fluorescence Photogrammetry

    NASA Technical Reports Server (NTRS)

    Dorrington, Adrian A.; Jones, Thomas W.; Danehy, Paul M.

    2004-01-01

    Laser-induced fluorescence target generation in dye-doped polymer films has recently been introduced as a promising alternative to more traditional photogrammetric targeting techniques for surface profiling of highly transparent or reflective membrane structures. We investigate the photophysics of these dye-doped polymers to help determine their long-term durability and suitability for laser-induced fluorescence photogrammetric targeting. These investigations included experimental analysis of the fluorescence emission pattern, spectral content, temporal lifetime, linearity, and half-life. Results are presented that reveal an emission pattern wider than normal Lambertian diffuse surface scatter, a fluorescence time constant of 6.6 ns, a pump saturation level of approximately 20 micro J/mm(exp 2), and a useful lifetime of more than 300,000 measurements. Furthermore, two demonstrations of photogrammetric measurements by laser-induced fluorescence targeting are presented, showing agreement between photogrammetric and physically measured dimensions within the measurement scatter of 100 micron.

  19. Structure and Properties of a Semi-crystalline Cationic Polymer for Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Beyer, Frederick; Price, Samuel; Savage, Alice; Ren, Xiaoming; Insane Membranes Collaboration

    Nafion has long been studied in order to understand its combination of good mechanical properties, chemical resistance, and excellent charge transport characteristics. In the past decade, uncertainty regarding the morphological behavior of Nafion has largely been resolved, allowing researchers to mimic and improve on the structure of this material. In this presentation, work to incorporate key characteristics of Nafion into a model cation-containing polymer will be described. In these new materials, semi-crystalline atactic poly(norbornene) is used to introduce good mechanical properties to anion-exchange membranes, analogous to the PTFE crystallites in Nafion. The ether linkages between the charged species and backbone are also utilized to place the cationic species (trimethylamine) in our materials into a mechanically soft environment. The resulting polymer shows some characteristics that are similar to those of Nafion. In this presentation, the synthesis, alkaline stability, mechanical properties, morphological behavior and charge transport properties will all be described.

  20. Tailoring the Separation Behavior of Polymer-Supported Organosilica Layered-Hybrid Membranes via Facile Post-Treatment Using HCl and HN3 Vapors.

    PubMed

    Gong, Genghao; Nagasawa, Hiroki; Kanezashi, Masakoto; Tsuru, Toshinori

    2016-05-01

    A promising layered-hybrid membrane consisting of a microporous organosilica active layer deposited onto a porous polymer support was prepared via a facile sol-gel spin-coating process. Subsequently, the pore sizes and structures of the organosilica top layers on the membrane surface were tuned at mild temperature combined with vapor treatment from either hydrochloric acid (HVT) or ammonia (AVT), thereby tailoring the desalination performance of the membranes during reverse osmosis (RO) processing. The effects of HVT and AVT on the pore size, structure, and morphology of organosilica layers and on the separation performances of membranes were investigated in detail. We confirmed that both HVT and AVT processes accelerated the condensation of silanol (Si-OH) in the organosilica layer, which led to dense silica networks. The layered-hybrid membranes after HVT showed an improved salt rejection and reduced water flux, while membranes after AVT exhibited a decrease in both salt rejection and water permeability. We found that HVT gave rise to smoother and denser organosilica layers, while AVT produced large voids and formed pinholes due to Ostwald ripening. These conclusions were supported by a comparative analysis of the results obtained via FTIR, TG-MS, SPM, and RO desalination. PMID:27070105

  1. Effect of porous polymer films (track membranes) on the isothermal evaporation kinetics of water

    NASA Astrophysics Data System (ADS)

    Novikov, S. N.; Ermolaeva, A. I.; Timoshenkov, S. P.; Korobova, N. E.; Goryunova, E. P.

    2016-06-01

    The kinetics of isothermal evaporation of distilled water that was in remote (10-15-mm) contact with porous polymer films (track membranes (TMs)) was studied by microgravimetry (derivatograph). When the H2O-TM system contained a disperse medium, the supramolecular structure of water changed, and the number of clusters (coherent domains) drastically decreased. The extraction of the light phase from liquid water was correlated with the chemisorption of H2O molecules containing the para-isomer of hydrogen, which predominantly form coherent domains of water.

  2. Photocurrent generation from thylakoid membranes on osmium-redox-polymer-modified electrodes.

    PubMed

    Hamidi, Hassan; Hasan, Kamrul; Emek, Sinan Cem; Dilgin, Yusuf; Åkerlund, Hans-Erik; Albertsson, Per-Åke; Leech, Dónal; Gorton, Lo

    2015-03-01

    Thylakoid membranes (TMs) are uniquely suited for photosynthesis owing to their distinctive structure and composition. Substantial efforts have been directed towards use of isolated photosynthetic reaction centers (PRCs) for solar energy harvesting, however, few studies investigate the communication between whole TMs and electrode surfaces, due to their complex structure. Here we report on a promising approach to generate photosynthesis-derived bioelectricity upon illumination of TMs wired with an osmium-redox-polymer modified graphite electrode, and generate a photocurrent density of 42.4 μA cm(-2). PMID:25703722

  3. Alkaline degradation studies of anion exchange polymers to enable new membrane designs

    NASA Astrophysics Data System (ADS)

    Nunez, Sean Andrew

    Current performance targets for anion-exchange membrane (AEM) fuel cells call for greater than 95% alkaline stability for 5000 hours at temperatures up to 120 °C. Using this target temperature of 120 °C, an incisive 1H NMR-based alkaline degradation method to identify the degradation products of n-alkyl spacer tetraalkylammonium cations in various AEM polymers and small molecule analogs. Herein, the degradation mechanisms and rates of benzyltrimethylammonium-, n-alkyl interstitial spacer- and n-alkyl terminal pendant-cations are studied on several architectures. These findings demonstrate that benzyltrimethylammonium- and n-alkyl terminal pendant cations are more labile than an n-alkyl interstitial spacer cation and conclude that Hofmann elimination is not the predominant mechanism of alkaline degradation. Additionally, the alkaline stability of an n-alkyl interstitial spacer cation is enhanced when combined with an n-alkyl terminal pendant. Interestingly, at 120 °C, an inverse trend was found in the overall alkaline stability of AEM poly(styrene) and AEM poly(phenylene oxide) samples than was previously shown at 80 °C. Successive small molecule studies suggest that at 120 °C, an anion-induced 1,4-elimination degradation mechanism may be activated on styrenic AEM polymers bearing an acidic alpha-hydrogen. In addition, an ATR-FTIR based method was developed to assess the alkaline stability of solid membranes and any added resistance to degradation that may be due to differential solubilities and phase separation. To increase the stability of anion exchange membranes, Oshima magnesate--halogen exchange was demonstrated as a method for the synthesis of new anion exchange membranes that typically fail in the presence of organolithium or Grignard reagents alone. This new chemistry, applied to non-resinous polymers for the first time, proved effective for the n-akyl interstitial spacer functionalization of poly(phenylene oxide) and poly(styrene- co

  4. Polymer electrolyte membrane fuel cell fault diagnosis based on empirical mode decomposition

    NASA Astrophysics Data System (ADS)

    Damour, Cédric; Benne, Michel; Grondin-Perez, Brigitte; Bessafi, Miloud; Hissel, Daniel; Chabriat, Jean-Pierre

    2015-12-01

    Diagnosis tool for water management is relevant to improve the reliability and lifetime of polymer electrolyte membrane fuel cells (PEMFCs). This paper presents a novel signal-based diagnosis approach, based on Empirical Mode Decomposition (EMD), dedicated to PEMFCs. EMD is an empirical, intuitive, direct and adaptive signal processing method, without pre-determined basis functions. The proposed diagnosis approach relies on the decomposition of FC output voltage to detect and isolate flooding and drying faults. The low computational cost of EMD, the reduced number of required measurements, and the high diagnosis accuracy of flooding and drying faults diagnosis make this approach a promising online diagnosis tool for PEMFC degraded modes management.

  5. Novel ceramic-polymer composite membranes for the separation of hazardous liquid waste. 1998 annual progress report

    SciTech Connect

    Cohen, Y.

    1998-06-01

    'This report summarizes the work progress over the last 1.75 years of a 3 year project. The objectives of the project have been to develop a new class of ceramic-supported polymeric membranes that could be tailored-designed for a wide-range of applications in remediation and pollution prevention. To date, a new class of chemically-modified ceramic membranes was developed for the treatment of oil-in-water emulsions and for the pervaporation removal of volatile organics from aqueous systems. These new ceramic-supported polymer (CSP) membranes are fabricated by modifying the pore surface of a ceramic membrane support by a graft polymerization process (Chaimberg and Cohen, 1994). The graft polymerization process consists of activating the membrane surface with alkoxy vinyl silanes onto which vinyl monomers are added via free-radical graft polymerization resulting in a thin surface layer of terminally anchored polymer chains. Reaction conditions are selected based on knowledge of the graft polymerization kinetics for the specific polymer/substrate system. The resultant ceramic-supported polymer (CSP) membrane is a composite structure in which mechanical strength is provided by the ceramic support and the selectivity is determined by the covalently bonded polymer brush layer. Thus, one of the unique attributes of the CSP membrane is that it can be used in environments where the polymer layer is swollen (or even completely miscible) in the mixture to be separated (Castro et al., 1993). It is important to note that the above modification process is carried out under mild conditions (e.g., temperature of about 70 C) and is well suited for large scale commercial application. In a series of studies, the applicability of a polyvinylpyrrolidone CSP membrane was demonstrated for the treatment of oil-in-water emulsion under a variety of flow conditions (Castro et al.,1996). Improved membrane performance was achieved due to minimization of surface adsorption of the oil components

  6. Proton conducting membrane for fuel cells

    DOEpatents

    Colombo, Daniel G.; Krumpelt, Michael; Myers, Deborah J.; Kopasz, John P.

    2007-03-27

    An ion conducting membrane comprising dendrimeric polymers covalently linked into a network structure. The dendrimeric polymers have acid functional terminal groups and may be covalently linked via linking compounds, cross-coupling reactions, or copolymerization reactions. The ion conducting membranes may be produced by various methods and used in fuel cells.

  7. Proton conducting membrane for fuel cells

    DOEpatents

    Colombo, Daniel G.; Krumpelt, Michael; Myers, Deborah J.; Kopasz, John P.

    2005-12-20

    An ion conducting membrane comprising dendrimeric polymers covalently linked into a network structure. The dendrimeric polymers have acid functional terminal groups and may be covalently linked via linking compounds, cross-coupling reactions, or copolymerization reactions. The ion conducting membranes may be produced by various methods and used in fuel cells.

  8. Durability and characterization studies of polymer electrolyte membrane fuel cell's coated aluminum bipolar plates and membrane electrode assembly

    NASA Astrophysics Data System (ADS)

    Hung, Y.; Tawfik, H.; Mahajan, D.

    Coated aluminum bipolar plates demonstrate better mechanical strength, ease of manufacturability, and lower interfacial contact resistance (ICR) than graphite composite plates in polymer electrolyte membrane (PEM) fuel cell applications. In this study, coated aluminum and graphite composite bipolar plates were installed in separate single PEM fuel cells and tested under normal operating conditions and cyclic loading. After 1000 h of operation, samples of both the bipolar plates and the membrane electrode assembly (MEA) were collected from both the cathode and the anode sides of the cell and characterized to examine the stability and integrity of the plate coating and evaluate possible changes of the ionic conductivity of the membrane due any electrochemical reaction with the coating material. Scanning electron microscope (SEM) and energy dispersive X-ray (EDX) analysis were performed on the land and valley surfaces of the reactant flow fields at both the anode and the cathode sides of the bipolar plates. The measurements were superimposed on the reference to identify possible zones of anomalies for the purpose of conducting focused studies in these locations. The X-ray diffraction (XRD) analysis of samples scraped from the anode and cathode electrodes of the MEA showed the tendency for catalyst growth that could result in power degradation. Samples of the by-product water produced during the single fuel cell operation were also collected and tested for the existence of chromium, nickel, carbon, iron, sulfur and aluminum using mass spectroscopy techniques. The EDX measurements indicated the possibility of dissociation and dissolution of nickel chrome that was used as the binder for the carbide-based corrosion-resistant coating with the aluminum substrate.

  9. Trimethylene carbonate and epsilon-caprolactone based (co)polymer networks: mechanical properties and enzymatic degradation.

    PubMed

    Bat, Erhan; Plantinga, Josée A; Harmsen, Martin C; van Luyn, Marja J A; Zhang, Zheng; Grijpma, Dirk W; Feijen, Jan

    2008-11-01

    High molecular weight trimethylene carbonate (TMC) and epsilon-caprolactone (CL) (co)polymers were synthesized. Melt pressed (co)polymer films were cross-linked by gamma irradiation (25 kGy or 50 kGy) in vacuum, yielding gel fractions of up to 70%. The effects of copolymer composition and irradiation dose on the cytotoxicity, surface properties, degradation behavior, and mechanical and thermal properties of these (co)polymers and networks were investigated. Upon incubation with cell culture medium containing extracts of (co)polymers and networks, human foreskin fibroblasts remained viable. For all (co)polymers and networks, cell viabilities were determined to be higher than 94%. The formed networks were flexible, with elastic moduli ranging from 2.7 to 5.8 MPa. Moreover, these form-stable networks were creep resistant under dynamic conditions. The permanent deformation after 2 h relaxation was as low as 1% after elongating to 50% strain for 20 times. The in vitro enzymatic erosion behavior of these hydrophobic (co)polymers and networks was investigated using aqueous lipase solutions. The erosion rates in lipase solution could be tuned linearly from 0.8 to 45 mg/(cm (2) x day) by varying the TMC to CL ratio and the irradiation dose. The copolymers and networks degraded essentially by a surface erosion mechanism. PMID:18855440

  10. Improved electrochemical in-situ characterization of polymer electrolyte membrane fuel cell stacks

    NASA Astrophysics Data System (ADS)

    Hartung, I.; Kirsch, S.; Zihrul, P.; Müller, O.; von Unwerth, T.

    2016-03-01

    In-situ diagnostics for single polymer electrolyte membrane fuel cells are well known and established. Comparable stack level techniques are urgently needed to enhance the understanding of degradation during real system operation, but have not yet reached a similar level of sophistication. We have therefore developed a new method for the quantification of the hydrogen crossover current in stacks, which in combination with a previously published technique now allows a clear quantitative characterization of the individual cells' membranes and electrodes. The limits of the reported methods are theoretically assessed and application is then demonstrated on automotive short stacks. The results prove to be highly reproducible and are validated for individual cells of the respective stacks by direct comparison with cyclic voltammetry results, showing good quantitative agreement for the hydrogen crossover current, the double layer capacitance and the electrochemically active surface area.

  11. Chaotic behavior of ion exchange phenomena in polymer gel electrolytes through irradiated polymeric membrane

    NASA Astrophysics Data System (ADS)

    Rawat, Sangeeta; Saha, Barnamala; Prasad, Awadhesh; Chandra, Amita

    2012-05-01

    A desktop experiment has been done to show the nonlinearity in the I-V characteristics of an ion conducting electrochemical micro-system. Its chaotic dynamics is being reported for the first time which has been captured by an electronic circuit. Polyvinylidene fluoride-co-hexafluoropropene (PVdF-HFP) gel electrolyte comprising of a combination of plasticizers (ethylene carbonate and propylene carbonate) and salts have been prepared to study the exchange of ions through porous polyethylene terephthalate (PET) membranes. The nonlinearity of this system is due to the ion exchange of the polymer gel electrolytes (PGEs) through a porous membrane. The different regimes of spiking and non-spiking chaotic motions are being presented. The possible applications are highlighted.

  12. Synthesis of polymers with the potential to release H 2S: Polydicyclopentadiene nanoporous membranes

    NASA Astrophysics Data System (ADS)

    Long, Tyler Richard

    This thesis discusses two very different projects. In the first project, synthesizing a polymer with the potential to release H2S. This was accomplished through the copolymerization of L-lactide and lactide monomers that has been functionalized with 4-hydroxythiobenzamide which is known to release H2S in vivo. The synthesis of the functionalized monomer required the development of a new method to attach functional groups to a derivative of L-lactide, which involved the addition of a thiol to an alpha- beta-unsaturated lactide using catalytic I2. After polymerization, the molecular weight of the copolymers ranged from 8 to 88 kg mol-1 with PDIs below 1.50. These polymers have the ability to be loaded with different amounts of thiobenzamide by controlling the ratio of the functionalized monomer with L-lactide during polymerization. The copolymers were fabricated into two sizes of microparticles with average diameters of 0.52 and 12 mum. The degradation of the smaller microparticles was studied in a PBS buffered solution at pH 7.4 which showed the slow release of the thiobenzamide over a 4 week period. These microparticles are the first to show potential to deliver H2S over a period of weeks. This research addresses a critical need in the field of H2S in medicine where no method exists to release H2S in vivo at times over a few hours. In the second project dicyclopentadiene was polymerized with Grubbs first generation catalyst and fabricated into highly cross-linked membranes with a thickness of 100 mum. The flux of twenty-one molecules with varying polarities and molecular weights ranging from 101 to 583 g mol-1 were studied. Molecules that permeated these membranes had flux rates of 10 -5 to 10-6 mol cm-2 h-1 but molecules that did not permeate these membranes had flux rates 10 4 to 105 times slower. The large difference in flux did not have a strong correlation to molecular weight or solubility in the membrane. However, there was a strong correlation to the cross

  13. Materials and characterization techniques for high-temperature polymer electrolyte membrane fuel cells

    PubMed Central

    2015-01-01

    Summary The performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) is critically dependent on the selection of materials and optimization of individual components. A conventional high-temperature membrane electrode assembly (HT-MEA) primarily consists of a polybenzimidazole (PBI)-type membrane containing phosphoric acid and two gas diffusion electrodes (GDE), the anode and the cathode, attached to the two surfaces of the membrane. This review article provides a survey on the materials implemented in state-of-the-art HT-MEAs. These materials must meet extremely demanding requirements because of the severe operating conditions of HT-PEMFCs. They need to be electrochemically and thermally stable in highly acidic environment. The polymer membranes should exhibit high proton conductivity in low-hydration and even anhydrous states. Of special concern for phosphoric-acid-doped PBI-type membranes is the acid loss and management during operation. The slow oxygen reduction reaction in HT-PEMFCs remains a challenge. Phosphoric acid tends to adsorb onto the surface of the platinum catalyst and therefore hampers the reaction kinetics. Additionally, the binder material plays a key role in regulating the hydrophobicity and hydrophilicity of the catalyst layer. Subsequently, the binder controls the electrode–membrane interface that establishes the triple phase boundary between proton conductive electrolyte, electron conductive catalyst, and reactant gases. Moreover, the elevated operating temperatures promote carbon corrosion and therefore degrade the integrity of the catalyst support. These are only some examples how materials properties affect the stability and performance of HT-PEMFCs. For this reason, materials characterization techniques for HT-PEMFCs, either in situ or ex situ, are highly beneficial. Significant progress has recently been made in this field, which enables us to gain a better understanding of underlying processes occurring during

  14. Popping balloons: formation of a crack network in rubber membranes

    NASA Astrophysics Data System (ADS)

    Moulinet, Sebastien; Adda-Bedia, Mokhtar; Equipe Morphogenèse et phénomènes multi-échelle Team

    2015-03-01

    Everyone can make the observation: a rubber balloon inflated until it spontaneously pop breaks into a large number of shreds. In contrast, a balloon pierced with a needle at an early stage of its inflation breaks into two large pieces. Using model latex balloons, we have experimentally investigated the transition between these two breaking regimes. We have showed that, above a threshold stress in the latex membrane, a single crack become unstable and separates into two new cracks. Then, a cascade of tip-splitting generates a network of cracks that eventually form a large number of fragments. We have observed that the instability of the crack occurs when it reaches a limit velocity that could the speed of sound. By studying the energy balance during the explosion, we can determine the intrinsic fracture energy of rubber, a measurement difficult to achieve with usual tensile testing.

  15. Synthesis and characterization of polymers and interpenetrating polymer networks (IPNs) with nonlinear optical (NLO) properties and related numerical studies

    NASA Astrophysics Data System (ADS)

    Sharma, P. R. Srikanth

    Copolymers of methyl methacrylate (MMA) and 2-propenoic acid, 2-methyl-, 2-[[[[4-methyl-3-[[[2-methyl-4-nitrophenyl)amino]carbonyl]aminophenyl]carbonyl]oxy]ethyl ester (PAMEE) exhibiting nonlinear optical (NLO) properties have been synthesized. Two kinds of urethane containing interpenetrating polymer networks (IPNs), consisting of nonlinear optical (NLO) chromophore, 2-methyl-4-nitroaniline (MNA) or Disperse Red1 (DR1) have been synthesized. The IPN systems consist of either aliphatic polycarbonate urethane (PCU) or 2,6-dimethyl-1,4-phenylene oxide (PPO) as one network and crosslinked poly (MMA-co-PAMEE) or poly (MMA-co-PMNEE) as the second network. Copolymers and interpenetrating polymer networks (IPNs) were characterized by IR spectroscopy, UV-VIS spectroscopy, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and second harmonic generation (SHG) measurements. The thin films of copolymers and IPNs were optically transparent and the corona poled polymers produced relatively large and stable SHG signals at room temperature. To understand the polarization decay of our NLO polymer we studied a simple theoretical model which can account for the main features which we observe. The addition of an apparent "chemical" reaction with a reaction activation energy EAB to the neighbor-facilitated Fredrickson-Anderson model shows the existence of a beta relaxation occurring simultaneously with the main alpha process. The combination of an Ising-model with antiferromagnetic interaction and the neighbor-facilitated Fredrickson-Anderson model allows a description of the polarization decay of polarized materials, such as our polymers, below the glass transition temperature Tg. The relaxation time for the polarization scales with the relaxation time of the alpha-process of the glass transition, and shows a typical curvature in the ln tau versus T-1 plot. Real polymers, such as poly(MMA-co-PAMEE) which we study possess both of these features and its

  16. Membrane resistance and current distribution measurements under various operating conditions in a polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Brett, D. J. L.; Atkins, S.; Brandon, N. P.; Vasileiadis, N.; Vesovic, V.; Kucernak, A. R.

    The ability to make spatially resolved measurements in a fuel cell provides one of the most useful ways in which to monitor and optimise their performance. Localised membrane resistance and current density measurements for a single channel polymer electrolyte fuel cell are presented for a range of operating conditions. The current density distribution results are compared with an analytical model that exhibited generally good agreement across a broad range of operating conditions. However, under conditions of high air flow rate, an increase in current is observed along the channel which is not predicted by the model. Under such circumstances, localised electrochemical impedance measurements show a decrease in membrane resistance along the channel. This phenomenon is attributed to drying of the electrolyte at the start of the channel and is more pronounced with increasing operating temperature. Under conditions of reactant depletion, an increase in electrolyte resistance with decreasing current is observed. This is due to the hydrating effect of product water and electro-osmotic drag through the membrane when ionic current is flowing. Localised conduction is shown to be an effective means of conditioning previously unused membrane electrode assemblies by forcing passage of ionic current through the electrolyte.

  17. Influence of Hydration Level on Polymer and Water Dynamics in Alkaline Anion Exchange Fuel Cell Membranes

    NASA Astrophysics Data System (ADS)

    Tarver, Jacob; Kim, Jenny; Tyagi, Madhu; Soles, Christopher; Tsai, Tsung-Han; Coughlin, Bryan

    2015-03-01

    Triblock copolymers based on poly(chloromethylstyrene)-b-poly(ethylene)-b-poly(chloromethylstyrene) can be quaternized to different extents to yield anion exchange membranes for alkaline fuel cells. In the absence of moisture, these membranes demonstrate bilayer lamellar morphology. Upon high levels of hydration, however, in-situ small angle neutron scattering reveals the emergence of higher-order diffraction peaks. This phenomena has previously been observed in analogous diblock copolymer-based membranes and has been attributed to the induction of a multilayer lamellar morphology in which selective striping of water occurs in the center of the ion-rich domain. By conducting humidity-resolved quasielastic neutron scattering (QENS) measurements using deuterated water, we are able to isolate differences in the pico- to nanosecond timescale dynamics of the hydrogenated membrane upon hydration. QENS measurements in the presence of a hydrogenated water source subsequently permit deconvolution and isolation of the translational and rotational dynamics of water as a function of relative humidity, revealing spatial and temporal changes in polymer and water motion at high levels of hydration.

  18. Synthesis and fuel cell characterization of blend membranes from phenyl phosphine oxide containing flourinated novel polymers

    NASA Astrophysics Data System (ADS)

    Gürtekin Seden, Merve; Baştürk, Emre; Inan, Tülay Y.; Kayaman Apohan, Nilhan; Güngör, Atilla

    2014-12-01

    Novel fluorinated poly(arylene ether)'s are synthesized from polycondensation of bis (p-hydroxy-tetrafluoro) phenyl) phenyl phosphine oxide (PFPPO-OH) with 4,4‧-dichlorodiphenyl sulfone (DCDPS) and 2,2-bis(4-hydroxyphenyl)propane (Bisfenol A) (Copolymer 1a) or 2,2-bis(4-hydroxyphenyl) hexafluoropropane (Bisphenol AF) (Copolymer 1b). The fluorinated copolymers have been blended with sulphonated poly(ether ether ketone)-SPEEK by solvent casting method. The water uptake and proton conductivity of the blend membranes decreases with the increase of copolymer content as expected, but proton conductivity values are still comparable to that of Nafion117® membrane. Addition of hydrophobic copolymer 1b to the SPEEK caused increase in water vapor transmission. Methanol permeability of the membranes is decreased to 8.2 × 10-8 cm2 s-1 and 1.3 × 10-9 cm2 s-1 by addition of Copolymer 1a and 1b, respectively and they are much lower than that of Nafion® 117 (1.21E-06 (cm2 s-1). The blend membranes endure up to 6.5 h before it starts to dissolve. Hydrogen and oxygen permeability of the blend membranes is one-hundredth of the Nafion®. Fluorinated polymer improved chemical, mechanical, and hydrolytic stability and also phenyl phosphine oxide structure in the ionomer increased the thermal stability, gas and methanol permeability and overcomed the drawbacks of the Nafion® type membranes.

  19. Highly stabilized, polymer-lipid membranes prepared on silica microparticles as stationary phases for capillary chromatography

    PubMed Central

    Gallagher, Elyssia S.; Adem, Seid M.; Baker, Christopher A.; Ratnayaka, Saliya N.; Jones, Ian W.; Hall, Henry K.; Saavedra, S. Scott; Aspinwall, Craig A.

    2015-01-01

    The ability to rapidly screen complex libraries of pharmacological modulators is paramount to modern drug discovery efforts. This task is particularly challenging for agents that interact with lipid bilayers or membrane proteins due to the limited chemical, physical, and temporal stability of conventional lipid-based chromatographic stationary phases. Here, we describe the preparation and characterization of a novel stationary phase material composed of highly stable, polymeric-phospholipid bilayers self-assembled onto silica microparticles. Polymer lipid membranes were prepared by photochemical or redox initiated polymerization of 1,2-bis[10-(2′,4′-hexadieoyloxy)decanoyl]-sn-glycero-2-phosphocholine (bis-SorbPC), a synthetic, polymerizable lipid. The resulting polymerized bis-SorbPC (poly(bis-SorbPC)) stationary phases exhibited enhanced stability compared to particles coated with 1,2-dioleoyl-sn-glycero-phosphocholine (unpolymerized) phospholipid bilayers when exposed to chemical (50mM triton X-100 or 50% acetonitrile) and physical (15 min sonication) insults after 30 days of storage. Further, poly(bis-SorbPC)-coated particles survived slurry packing into fused silica capillaries, compared to unpolymerized lipid membranes, where the lipid bilayer was destroyed during packing. Frontal chromatographic analyses of the lipophilic small molecules acetylsalicylic acid, benzoic acid, and salicylic acid showed > 44% increase in retention times (P < 0.0001) for all analytes on poly(bis-SorbPC)-functionalized stationary phase compared to bare silica microspheres, suggesting a lipophilic retention mechanism. Phospholipid membrane-functionalized stationary phases that withstand the chemical and physical rigors of capillary LC conditions can substantially increase the efficacy of lipid membrane affinity chromatography, and represents a key advance towards the development of robust membrane protein-functionalized chromatographic stationary phases. PMID:25670414

  20. Pattern Formations in Polymer-Molecular Motor Networks

    NASA Astrophysics Data System (ADS)

    Smith, David; Humphrey, David; Duggan, Cynthia; Käs, Josef

    2001-03-01

    In previous studies with the microtubule-kinesin system, organized patterns such as asters and rotating vortices have been seen (Nedelec et al, Nature 1997), which were of a dynamic nature and dependent on active motors. A similar system was constructed using actin and myosin, which displays similar patterns, however, with drastically different dynamics. These patterns arise independent of the initial amount of immediate use energy (in the form of ATP), assembling only upon the near exhaustion of available ATP. Further studies have clearly shown that in fact these patterns are not dependent upon the motor activity of the myosin but its propensity to serve as a cross-linking element in an actin network, with the motor activity serving to prevent the arising of order in the system. We believe the dynamic differences inherent between the two polymer-motor systems studied lies primarily in the structural nature of the motor complexes, with the kinesin complex ordering the system by pushing multiple filaments in a parallel direction, and the myosin complexes disordering the system by pushing filaments in an antiparallel manner.

  1. Properties of poly(ethylene terephthalate) track membranes with a polymer layer obtained by plasma polymerization of pyrrole vapors

    NASA Astrophysics Data System (ADS)

    Kravets, L.; Dmitriev, S.; Lizunov, N.; Satulu, V.; Mitu, B.; Dinescu, G.

    2010-03-01

    The structure and the charge transport properties of poly(ethylene terephthalate) track membrane modified by pyrrole plasma were studied. It was found that polymer deposition on the surface of a track membrane via plasma polymerization of pyrrole results in the creation of composite nanomembranes that, in the case of the formation of a semipermeable layer, possess asymmetric conductivity in electrolyte solutions - a rectification effect similar to that of a p-n junction in semiconductors. It is caused by presence in the membranes of two layers with different functional groups and also by the pore geometry. Such membranes can be used to create chemical and biochemical sensors.

  2. Dually cross-linked polymer electrolyte membranes for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    End-group crosslinkable sulfonated poly(arylene ether sulfone) copolymer (ESPAES) and imidazolium poly(arylene ether sulfone) copolymer (IPAES) are synthesized as a proton exchange membrane and ionic crosslinker, respectively. A novel dually cross-linked membrane (DCM) based on ESPAES is similar to an inter-penetrating network and is prepared via blending IPAES and thermal treatment for direct methanol fuel cell (DMFC) applications. The synergistic effects of end-group crosslinking and ionic crosslinking improve chemical and thermal stability and mechanical properties. In addition, the DMFC performance of the DCM outperforms that of the end-group cross-linked SPAES and Nafion® 212 due to its excellent fuel barrier property in spite of relatively low proton conductivity, which is derived from the content of the non-proton conducting IPAES copolymer. Consequently, the DCM has great potential as an electrolyte membrane for DMFC applications.

  3. Probing Rubber Cross-Linking Generation of Industrial Polymer Networks at Nanometer Scale.

    PubMed

    Gabrielle, Brice; Gomez, Emmanuel; Korb, Jean-Pierre

    2016-06-23

    We present improved analyses of rheometric torque measurements as well as (1)H double-quantum (DQ) nuclear magnetic resonance (NMR) buildup data on polymer networks of industrial compounds. This latter DQ NMR analysis allows finding the distribution of an orientation order parameter (Dres) resulting from the noncomplete averaging of proton dipole-dipole couplings within the cross-linked polymer chains. We investigate the influence of the formulation (filler and vulcanization systems) as well as the process (curing temperature) ending to the final polymer network. We show that DQ NMR follows the generation of the polymer network during the vulcanization process from a heterogeneous network to a very homogeneous one. The time variations of microscopic Dres and macroscopic rheometric torques present power-law behaviors above a threshold time scale with characteristic exponents of the percolation theory. We observe also a very good linear correlation between the kinetics of Dres and rheometric data routinely performed in industry. All these observations confirm the description of the polymer network generation as a critical phenomenon. On the basis of all these results, we believe that DQ NMR could become a valuable tool for investigating in situ the cross-linking of industrial polymer networks at the nanometer scale. PMID:27254797

  4. Ultrathin, freestanding, stimuli-responsive, porous membranes from polymer hydrogel-brushes

    NASA Astrophysics Data System (ADS)

    Kang, Chengjun; Ramakrishna, Shivaprakash N.; Nelson, Adrienne; Cremmel, Clement V. M.; Vom Stein, Helena; Spencer, Nicholas D.; Isa, Lucio; Benetti, Edmondo M.

    2015-07-01

    The fabrication of freestanding, sub-100 nm-thick, pH-responsive hydrogel membranes with controlled nano-morphology, based on modified poly(hydroxyethyl methacrylate) (PHEMA) is presented. Polymer hydrogel-brush films were first synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequently detached from silicon substrates by UV-induced photo-cleavage of a specially designed linker within the initiator groups. The detachment was also assisted by pH-induced osmotic forces generated within the films in the swollen state. The mechanical properties and morphology of the freestanding films were studied by atomic force microscopy (AFM). Inclusion of nanopores of controlled diameter was accomplished by performing SI-ATRP from initiator-coated surfaces that had previously been patterned with polystyrene nanoparticles. Assembly parameters and particle sizes could be varied, in order to fabricate nanoporous hydrogel-brush membranes with tunable pore coverage and characteristics. Additionally, due to the presence of weak polyacid functions within the hydrogel, the membranes exhibited pH-dependent thickness in water and reversible opening/closing of the pores.The fabrication of freestanding, sub-100 nm-thick, pH-responsive hydrogel membranes with controlled nano-morphology, based on modified poly(hydroxyethyl methacrylate) (PHEMA) is presented. Polymer hydrogel-brush films were first synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequently detached from silicon substrates by UV-induced photo-cleavage of a specially designed linker within the initiator groups. The detachment was also assisted by pH-induced osmotic forces generated within the films in the swollen state. The mechanical properties and morphology of the freestanding films were studied by atomic force microscopy (AFM). Inclusion of nanopores of controlled diameter was accomplished by performing SI-ATRP from initiator-coated surfaces that had

  5. Fabrication of cell outer membrane mimetic polymer brush on polysulfone surface via RAFT technique

    NASA Astrophysics Data System (ADS)

    Ma, Qian; Zhang, Hui; Zhao, Jiang; Gong, Yong-Kuan

    2012-10-01

    Cell membrane mimetic antifouling polymer brush was grown on polysulfone (PSF) membrane by surface-induced reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC). The RAFT agent immobilized PSF substrate was prepared by successive chloromethylation, amination with ethylenediamine (EDA) and amidation of the amine group of grafted EDA with the carboxylic group of 4-cyanopentanoic acid dithiobenzoate (CPAD). The surface RAFT polymerization of MPC was initiated in aqueous solution by 4,4‧-azobis-4-cyanopentanoic acid (ACPA). The formation of PMPC brush coating is evidenced by X-ray photoelectron spectroscopy and water contact angle measurements. The degree of polymerization of PMPC and the polymer grafting density were calculated from the high resolution XPS spectra. The platelet adhesion and protein adsorption results showed that the PMPC-grafted PSF surface has excellent antifouling ability to resist platelet adhesion completely and suppress protein adsorption significantly. This biomimetic and bio-friendly surface RAFT polymerization strategy could be promising for a variety of biomedical applications.

  6. Enhancement in biological response of Ag-nano composite polymer membranes using plasma treatment for fabrication of efficient bio materials

    NASA Astrophysics Data System (ADS)

    Agrawal, Narendra Kumar; Sharma, Tamanna Kumari; Chauhan, Manish; Agarwal, Ravi; Vijay, Y. K.; Swami, K. C.

    2016-05-01

    Biomaterials are nonviable material used in medical devices, intended to interact with biological systems, which are becoming necessary for the development of artificial material for biological systems such as artificial skin diaphragm, valves for heart and kidney, lenses for eye etc. Polymers having novel properties like antibacterial, antimicrobial, high adhesion, blood compatibility and wettability are most suitable for synthesis of biomaterial, but all of these properties does not exist in any natural or artificial polymeric material. Nano particles and plasma treatment can offer these properties to the polymers. Hence a new nano-biomaterial has been developed by modifying the surface and chemical properties of Ag nanocomposite polymer membranes (NCPM) by Argon ion plasma treatment. These membranes were characterized using different techniques for surface and chemical modifications occurred. Bacterial adhesion and wettability were also tested for these membranes, to show direct use of this new class of nano-biomaterial for biomedical applications.

  7. Optimization and Characterization of Self-assembled Triblock Polymer Membranes with Chemically-Tunable Pore Walls for Nanofiltration Applications

    NASA Astrophysics Data System (ADS)

    Sargent, Jessica; Mulvenna, Ryan; Prato, Rafael; Weidman, Jacob; Phillip, William; Boudouris, Bryan

    2015-03-01

    The field of block polymer-based membranes for separation applications has grown considerably in the past several years. However, decreasing the domain sizes of these membranes to below 5 nm has proven to be a challenge in many instances. Here, we demonstrate that a triblock polymer, polyisoprene- b-polystyrene- b-poly(tert-butyl methacrylate) (PI-PS-PtBMA), can be utilized to form nanoporous membranes capable of high flux and high selectivity based on both size and chemical composition. By controlling the synthesis, solution self-assembly, and non-solvent induced phase separation of these polymers, a scalable fabrication process can produce thin-film membranes that feature monodisperse pores approaching 1 nm in diameter, tunable pore-wall chemistry, good mechanical stability, and chlorine degradation resistance. The PtBMA functionality can further be converted to a number of side chain functionalities through simple coupling chemistry to produce membranes with specific chemical and structural characteristics tailored to meet the needs of various applications. In particular, these membranes provide a promising, inexpensive platform for chlorine degradation and fouling-resistant membranes for water purification that can be produced on an industrial scale.

  8. Biodegradability of regenerated cellulose films coated with polyurethane/natural polymers interpenetrating polymer networks

    SciTech Connect

    Zhang, L.; Zhou, J.; Huang, J.; Gong, P. Zhou, Q.; Zheng, L.; Du, Y.

    1999-11-01

    Interpenetrating polymer network (IPN) coatings synthesized from castor-oil-based polyurethane (PU) with chitosan, nitrocellulose, or elaeostearin were coated on regenerated cellulose (RC) film for curing at 80--100 C for 2--5 min, providing biodegradable, water-resistant cellulose films coded, respectively, as RCCH, RCNC, and RCEs. The coated films were buried in natural soil for decaying and inoculated with a spore suspension of fungi on the agar medium, respectively, to test biodegradability. The viscosity-average molecular weight, M{sub {eta}}, and the weight of the degraded films decreased sharply with the progress of degradation. The degradation half-lifes, t{sub 1/2}, of the films in soil at 30 C were found to be 19 days for RC, 25 days for RCNC, 32 days for RCCH, and 45 days for the RCEs films. Scanning electron microscopy (SEM) showed that the extent of decay followed in the order RC {gt} RCNC {gt} RCCH {gt} RCEs. SEM, infrared (IR), high-performance liquid chromatography (HPLC), and CO{sub 2} evolution results indicated that the microorganisms directly attacked the water-resistant coating layer and then penetrated into the cellulose to speedily metabolize, while accompanying with producing CO{sub 2}, H{sub 2}O, glucose cleaved from cellulose, and small molecules decomposed from the coatings.

  9. Rotational isomeric state theory applied to the stiffness prediction of an anion polymer electrolyte membrane

    SciTech Connect

    Gao, Fei; Weiland, L.M.; Kitchin, J.R.

    2008-05-01

    While the acidic polymer electrolyte membrane (PEM) Nafion® has garnered considerable attention, the active response of basic PEMs offers another realm of potential applications. For instance, the basic PEM Selemion® is currently being considered in the development of a CO2 separation prototype device to be employed in coal power plant flue gas. The mechanical integrity of this material and subsequent effects in active response in this harsh environment will become important in prototype development. A multiscale modeling approach based on rotational isomeric state theory in combination with a Monte Carlo methodology may be employed to study mechanical integrity. The approach has the potential to be adapted to address property change of any PEM in the presence of foreign species (reinforcing or poisoning), as well as temperature and hydration variations. The conformational characteristics of the Selemion® polymer chain and the cluster morphology in the polymer matrix are considered in the prediction of the stiffness of Selemion® in specific states.

  10. Comparative study on the interaction of cell-penetrating polycationic polymers with lipid membranes.

    PubMed

    Takechi, Yuki; Tanaka, Hirokazu; Kitayama, Hiroki; Yoshii, Haruka; Tanaka, Masafumi; Saito, Hiroyuki

    2012-01-01

    Cell-penetrating peptides are arginine- and lysine-rich cationic peptides that can readily enter cells not only by themselves but also carrying other macromolecular cargos. In fact, we have reported that polycationic polymer such as poly-l-lysine (PLL) and poly-l-arginine (PLA) translocate through negatively charged phospholipid liposome membranes. In this work, we made a comparative study of the interaction of PLL or PLA with lipid membranes consisting of negatively charged phospholipids to understand the role of basic amino acid residue (i.e. arginine and lysine) in the membrane-penetrating activity of polypeptides. PLA and PLL translocated into giant unilamellar vesicle composed of soybean phospholipids. ζ-potential and turbidity measurements demonstrated the electrostatic binding of PLL and PLA to large unilamellar vesicle (LUV). Fluorescence studies using membrane probes revealed that the binding of PLA and PLL to LUV affects the hydration and packing of the membrane interface region, in which the membrane insertion of PLA appeared to be greater than PLL. Differential scanning calorimetry showed that the enthalpy of the gel to liquid-crystalline phase transition for dipalmitoyl phosphatidylglycerol vesicle was greatly reduced by binding of PLL and PLA, in which the reduction is much larger in PLA than in PLL. Circular dichroism measurements in 2,2,2-trifluoroethanol/water mixture or in the presence of LUV indicated that the propensity of PLA to form α-helical structure is greater than PLL. Consistently, attenuated total reflection-Fourier transform infrared spectroscopy revealed that there is greater α-helical structure in PLA bound to LUV compared to PLL, which has much less ordered structure. Furthermore, isothermal titration calorimetry measurements demonstrated that the contribution of enthalpy to the energetics of binding to LUV is two-fold larger in PLA than in PLL. These results suggest that the stronger interaction of arginine residue with

  11. Hybrid polymer networks as ultra low `k` dielectric layers

    DOEpatents

    Lewicki, James; Worsley, Marcus A.

    2016-02-16

    According to one embodiment, a polymeric material includes at least one polydimethylsiloxane (PDMS) polymer, and at least one polyhedral oligomericsilsequioxane (POSS) molecule. According to another embodiment, a method includes providing at least one polydimethylsiloxane (PDMS) polymer, providing at least one polyhedral oligomericsilsequioxane (POSS) molecule, and coupling the at least one PDSM polymer to the at least one POSS molecule to form a hybrid polymeric material.

  12. Synthesis and characterization of sulfonated poly(ether sulfone)s containing mesonaphthobifluorene for polymer electrolyte membrane fuel cell.

    PubMed

    Lim, Youngdon; Seo, Dongwan; Lee, Soonho; Hossain, Md Awlad; Lim, Jinseong; Lee, Sangyoung; Hong, Taehoon; Kim, Whangi

    2014-10-01

    The novel sulfonated poly(ether sulfone)s containing mesonaphthobifluorene (MNF) moiety were synthesized and characterized their properties. The prepared polymers have highly conjugated aromatic structure due to the MNF group which is an allotrope of carbon and one atom thick planar sheets of sp2-bonded carbon atoms. Poly(ether sulfone)s bearing tetraphenylethylene on polymer backbone were synthesized by polycondensation and followed intra-cyclization from tetraphenylethylene to form MNF by Friedel-craft reaction with Lewis acid (FeCl3). The sulfonation was performed selectively on MNF units with conc. sulfuric acid. The structural properties of the sulfonated polymers were investigated by 1H-NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, and proton conductivity. The synthesized polymer electrolyte membranes showed better thermal and dimensional stabilities owing to the inducted highly conjugated aromatic structure in the polymer backbone. The water uptake of the synthesized membranes ranged from 23-52%, compared with 32.13% for Nafion 211 at 80 degrees C. The synthesized membranes exhibited proton conductivities (80 degrees C, RH 90%) of 74.6-100.4 mS/cm, compared with 102.7 mS/cm for Nafion 211. PMID:25942900

  13. Design and Development of Highly Sulfonated Polymers as Proton Exchange Membranes for High Temperature Fuel Cell Applications

    NASA Astrophysics Data System (ADS)

    Dang, Thuy D.; Bai, Zongwu; Yoonessi, Mitra

    A series of high molecular weight, highly sulfonated poly(arylenethioethersulfone) (SPTES) polymers were synthesized by polycondensation, which allowed controlled sulfonation of up to 100 mol %. The SPTES polymers were prepared via step growth polymerization of sulfonated aromatic difluorosulfone, aromatic difluorosulfone, and 4,4 '-thiobisbenzenthiol in sulfolane solvent at the temperature up to 180 °C. The composition and incorporation of the sulfonated repeat unit into the polymers were confirmed by 1H nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. Solubility tests on the SPTES polymers confirmed that no cross-linking and probably no branching occurred during the polymerizations. The end-capping groups were introduced in the SPTES polymers to control the molecular weight distribution and reduce the water solubility of the polymers. Tough, ductile membranes formed via solvent-casting exhibited increased water absorption with increasing degrees of sulfonation. The polymerizations conducted with the introduction of end-capping groups resulted in a wide variation in polymer proton conductivity, which spanned a range of 100 -300 mS cm-1, measured at 65 °C and 85 % relative humidity. The measured proton conductivities at elevated temperatures and high relative humidities are up to three times higher than that of the state-of-the-art Nafion-H proton exchange membrane under nearly comparable conditions. The thermal and mechanical properties of the SPTES polymers were investigated by TGA, DMA, and tensile measurements. The SPTES polymers show high glass transition temperatures (Tg), ˜220 °C, depending on the degree of sulfonation in polymerization. SPTES-50 polymer shows a Tg of 223 °C, with high tensile modulus, high tensile strengths at break and at yield as well as elongation at break. Wide angle X-ray scattering of the polymers shows two broad scattering features centered at 4.5 Å and 3.3 Å, the latter peak being

  14. Direct Sensing of Total Acidity by Chronopotentiometric Flash Titrations at Polymer Membrane Ion-Selective Electrodes

    PubMed Central

    Gemene, Kebede L.; Bakker, Eric

    2008-01-01

    Polymer membrane ion-selective electrodes containing lipophilic ionophores are traditionally interrogated by zero current potentiometry, which, ideally, gives information on the sample activity of ionic species. It is shown here that a discrete cathodic current pulse across an H+-selective polymeric membrane doped with the ionophore ETH 5294 may be used for the chronopotentiometric detection of pH in well buffered samples. However, a reduction in the buffer capacity leads to large deviations from the expected Nernstian response slope. This is explained by the local depletion of hydrogen ions at the sample-membrane interface as a result of the galvanostatically imposed ion flux in direction of the membrane. This depletion is found to be a function of the total acidity of the sample and can be directly monitored chronopotentiometrically in a flash titration experiment. The subsequent application of a baseline potential pulse reverses the extraction process of the current pulse, allowing one to interrogate the sample with minimal perturbation. In one protocol, total acidity is found to be proportional to the magnitude of applied current at the flash titration endpoint. More conveniently, the square root of the flash titration endpoint time observed at a fixed applied current is a linear function of the total acid concentration. This suggests that it is possible to perform rapid localized pH titrations at ion-selective electrodes without the need for volumetric titrimetry. The technique is explored here for acetic acid, MES and citric acid with promising results. Polymeric membrane electrodes on the basis of poly(vinyl chloride) plasticized with o-nitrophenyloctylether in a 1:2 mass ratio may be used for the detection of acids of up to ca. 1 mM concentration, with flash titration times on the order of a few seconds. Possible limitations of the technique are discussed, including variations of the acid diffusion coefficients and influence of electrical migration. PMID

  15. Analytical theory of polymer-network-mediated interaction between colloidal particles

    PubMed Central

    Di Michele, Lorenzo; Zaccone, Alessio; Eiser, Erika

    2012-01-01

    Nanostructured materials based on colloidal particles embedded in a polymer network are used in a variety of applications ranging from nanocomposite rubbers to organic-inorganic hybrid solar cells. Further, polymer-network-mediated colloidal interactions are highly relevant to biological studies whereby polymer hydrogels are commonly employed to probe the mechanical response of living cells, which can determine their biological function in physiological environments. The performance of nanomaterials crucially relies upon the spatial organization of the colloidal particles within the polymer network that depends, in turn, on the effective interactions between the particles in the medium. Existing models based on nonlocal equilibrium thermodynamics fail to clarify the nature of these interactions, precluding the way toward the rational design of polymer-composite materials. In this article, we present a predictive analytical theory of these interactions based on a coarse-grained model for polymer networks. We apply the theory to the case of colloids partially embedded in cross-linked polymer substrates and clarify the origin of attractive interactions recently observed experimentally. Monte Carlo simulation results that quantitatively confirm the theoretical predictions are also presented. PMID:22679289

  16. Interpenetrating polymer network approach to tougher and more microcracking resistant high temperature polymers. I - LaRC-RP40

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H.; Morgan, Cassandra D.

    1988-01-01

    Interpenetrating polymer networks in the form of the LaRC-RP40 resin, prepared by the in situ polymerization of a thermosetting imide prepolymer and thermoplastic monomer reactants, are presently used to obtain toughness and microcracking resistance in a high-temperature polymer. Attention is presently given to the processing, physical, and mechanical properties, as well as the thermooxidative stability, of both the neat resin and the resin as a graphite fiber-reinforced matrix. Microcracking after thermal cycling was also tested. LaRC-RP40 exhibits significant resin fracture toughness improvements over the PMR-15 high-temperature matrix resin.

  17. A composite membrane based on a biocompatible cellulose as a host of gel polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Xiao, S. Y.; Yang, Y. Q.; Li, M. X.; Wang, F. X.; Chang, Z.; Wu, Y. P.; Liu, X.

    2014-12-01

    A composite polymer membrane is prepared by coating poly(vinylidene fluoride) (PVDF) on the surface of a membrane based on methyl cellulose (MC) which is environmentally friendly and cheap. Its characteristics are investigated by scanning electron microscopy, FT-IR, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The outer PVDF layers are porous which results in high electrolyte uptake and the lithium ion transference number is much larger than that of the pure MC. Moreover, the cell based on Li//LiFePO4 delivers high discharge capacity and good rate behavior in the range of 4.2-2.5 V when the composite membrane is used as the separator and the host of a gel polymer electrolyte, lithium as the counter and reference electrode, and LiFePO4 as cathode. The obtained results suggest that this unique composite membrane shows great attraction in the lithium ion batteries with high safety and low cost.

  18. Formation of Polymer Networks for Fast In-Plane Switching of Liquid Crystals at Low Temperatures

    NASA Astrophysics Data System (ADS)

    Yu, Byeong-Hun; Song, Dong Han; Kim, Ki-Han; Wok Park, Byung; Choi, Sun-Wook; Park, Sung Il; Kang, Sung Gu; Yoon, Jeong Hwan; Kim, Byeong Koo; Yoon, Tae-Hoon

    2013-09-01

    We formed a polymer structure to enable fast in-plane switching of liquid crystals at low temperatures. The problem of the inevitable slow response at low temperatures was reduced by the formation of in-cell polymer networks in in-plane switching (IPS) cells. The electro-optic characteristics of polymer-networked IPS cells were measured at temperatures ranging from -10 to 20 °C. The turn-on and turn-off times of an IPS cell were reduced by 44.5 and 47.2% at -10 °C by the formation of polymer networks. We believe that the proposed technology can be applied to emerging display devices such as mobile phones and automotive displays that may be used at low temperatures.

  19. Free-Standing, Nanopatterned Janus Membranes of Conducting Polymer-Virus Nanoparticle Arrays.

    PubMed

    Tiu, Brylee David B; Tiu, Sicily B; Wen, Amy M; Lam, Patricia; Steinmetz, Nicole F; Advincula, Rigoberto C

    2016-06-21

    Nanostructured mesoscale materials find wide-ranging applications in medicine and energy. Top-down manufacturing schemes are limited by the smallest dimension accessible; therefore, we set out to study a bottom-up approach mimicking biological systems, which self-assemble into systems that orchestrate complex energy conversion functionalities. Inspired by nature, we turned toward protein-based nanoparticle structures formed by plant viruses, specifically the cowpea mosaic virus (CPMV). We report the formation of hierarchical CPMV nanoparticle assemblies on colloidal-patterned, conducting polymer arrays using a protocol combining colloidal lithography, electrochemical polymerization, and electrostatic adsorption. In this approach, a hexagonally close-packed array of polystyrene microspheres was assembled on a conductive electrode to function as the sacrificial colloidal template. A thin layer of conducting polypyrrole material was electrodeposited within the interstices of the colloidal microspheres and monitored in situ using electrochemical quartz crystal microbalance with dissipation (EC-QCM-D). Etching the template revealed an inverse opaline conducting polymer pattern capable of forming strong electrostatic interactions with CPMV and therefore enabling immobilization of CPMV on the surface. The CPMV-polymer films were characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Furthermore, molecular probe diffusion experiments revealed selective ion transport properties as a function of the presence of the CPMV nanoparticles on the surface. Lastly, by utilizing its electromechanical behavior, the polymer/protein membrane was electrochemically released as a free-standing film, which can potentially be used for developing high surface area cargo delivery systems, stimuli-responsive plasmonic devices, and chemical and biological sensors. PMID:27244119

  20. Tuning the Photoinduced Motion of Glassy Azobenzene Polymers and Networks

    NASA Astrophysics Data System (ADS)

    Vaia, R. A.

    2013-03-01

    Continual innovation at the forefront of soft-matter, in areas such as liquid crystal networks, nano-composites and bio-molecules, is providing exciting opportunities to create smart materials systems that exhibit a controlled, reproducible and reversible modulation of physical properties. These material systems evoke the adaptivity of natural organisms, and inspire radical aerospace notions. A key example is photo-responsive polymers, which convert a light stimulus input into a mechanical output (work). Photoinduced conformational changes, such as within azobenzene, dictate molecular-level distortions that summate into a macroscopic strain, which often manifests as a shape change or motion. The transduction of the molecular-level response to a macroscale effect is regulated by mesoscopic features, such as chain packing, free volume, and local molecular order - factors which depend on chemical composition as well as the process history of the material. For example, physical aging increases the density of the glass, reduces local free volume, and thus decreases the minima in local conformation space which strongly influences the azobenzene photochemistry (trans-cis-trans isomerization). The subsequent change in the energy landscape of the system reduces the fraction of azobenzene able to undergo reconfiguration as well as increases the probability that those photoinduced conformations will relax back to the initial local environment. The result is a tuning of the magnitude of macroscopic strain and the ability to shift from shape fixing to shape recovery, respectively. Work done in collaboration with H. Koerner, K.M. Lee, M. Smith, D. Wang, L-S. Tan. and T. White, Air Force Research Laboratory.

  1. Novel ceramic-polymer composite membranes for the separation of liquid waste. Annual progress report, September 15, 1996--September 14, 1997

    SciTech Connect

    Cohen, Y.

    1997-01-01

    'The project on ceramic-supported polymer membranes focuses on the development of a novel class of membranes for the separation of organics from both organic-aqueous and organic-organic mixtures, Theses membranes are fabricated by a graft polymerization process where polymer chains are grown onto the surface of a ceramic support membrane. The surface graft polymerization process, developed at UCLA, results in the formation of a thin polymer layer covalently bonded to the membrane pore surface as a layer of terminally anchored polymeric chains. Through the selection of the polymer most appropriate for the desired separation task, the graft polymerized surface layer can be synthesized to impart specific separation properties to the membrane. It is expected that this project will lead to the demonstration of a new technology for the tailor design of a new class of selective and robust ceramic-supported polymer membranes. This new approach will allow the rapid deployment of task-specific membranes for the separation of waste constituents for subsequent recovery, treatment or disposal. Progress to date includes the preparation of successful silica-polyvinylpyrrolidone (PVP) membrane for the treatment of oil-in-water emulsions and a silica-polyvinylacetate (PVAc) pervaporation membrane for the separation of organics from water. Current work is ongoing to study the performance of the pervaporation membrane for the removal of chlorinated organics from water and to develop a pervaporation membrane for organic-organic separation. In another aspect of the study, the authors are studying the hydrophilic PVP CSP membrane for oil-in-water emulsion treatment with the goal of determining the optimal membrane polymer surface structure as a function of various operating conditions (e.g., tube-side Reynolds number and transmembrane pressure), Work is also in progress to characterize the polymer layer by AFM and internal reflection FTIR, and to model the conformation of the polymer

  2. Ultrathin, freestanding, stimuli-responsive, porous membranes from polymer hydrogel-brushes.

    PubMed

    Kang, Chengjun; Ramakrishna, Shivaprakash N; Nelson, Adrienne; Cremmel, Clement V M; vom Stein, Helena; Spencer, Nicholas D; Isa, Lucio; Benetti, Edmondo M

    2015-08-14

    The fabrication of freestanding, sub-100 nm-thick, pH-responsive hydrogel membranes with controlled nano-morphology, based on modified poly(hydroxyethyl methacrylate) (PHEMA) is presented. Polymer hydrogel-brush films were first synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequently detached from silicon substrates by UV-induced photo-cleavage of a specially designed linker within the initiator groups. The detachment was also assisted by pH-induced osmotic forces generated within the films in the swollen state. The mechanical properties and morphology of the freestanding films were studied by atomic force microscopy (AFM). Inclusion of nanopores of controlled diameter was accomplished by performing SI-ATRP from initiator-coated surfaces that had previously been patterned with polystyrene nanoparticles. Assembly parameters and particle sizes could be varied, in order to fabricate nanoporous hydrogel-brush membranes with tunable pore coverage and characteristics. Additionally, due to the presence of weak polyacid functions within the hydrogel, the membranes exhibited pH-dependent thickness in water and reversible opening/closing of the pores. PMID:26169114

  3. Profiling measurements of metal ion distribution in thin polymer inclusion membranes by Rutherford backscattering spectrometry

    NASA Astrophysics Data System (ADS)

    Guedioura, B.; Bendjaballah, N.; Alioui, N.

    2014-05-01

    Polymer inclusion membranes (PIMs) composed of a homogeneous mixture of cellulose triacetate matrix, 2-nitro-phenyl-octyl-ether as plasticizer and tri-octyl-phosphine-oxyde as carrier were synthesized by the spin coating method. Synthesized membranes were doped with molybdenum metal ions and then characterized by four experimental techniques: thermo gravimetric and differential analyses, scanning electron microscopy (SEM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and Rutherford backscattering (RBS) spectrometry using a 3.2 MeV He+ ion beam. The RBS analysis has established both the elemental composition as well as the Mo+ metal profiling of the studied PIMs. The experimental irradiation conditions were optimized in order to determine the ion fluence thresholds resulting in measurable changes in elemental composition of membranes. Changes in physico-chemical properties of the irradiated PIMs vs He+ ion fluence were observed with the ATR-FTIR analysis. Also, the SEM analysis of PIMs surfaces has revealed a porous texture, while the thermal analysis of annealed PIMs at 105°C has showed no significant changes of mass (∼1%) of the studied samples.

  4. Preparation and Characterization of Nanocomposite Polymer Membranes Containing Functionalized SnO2 Additives

    PubMed Central

    Scipioni, Roberto; Gazzoli, Delia; Teocoli, Francesca; Palumbo, Oriele; Paolone, Annalisa; Ibris, Neluta; Brutti, Sergio; Navarra, Maria Assunta

    2014-01-01

    In the research of new nanocomposite proton-conducting membranes, SnO2 ceramic powders with surface functionalization have been synthesized and adopted as additives in Nafion-based polymer systems. Different synthetic routes have been explored to obtain suitable, nanometer-sized sulphated tin oxide particles. Structural and morphological characteristics, as well as surface and bulk properties of the obtained oxide powders, have been determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopies, N2 adsorption, and thermal gravimetric analysis (TGA). In addition, dynamic mechanical analysis (DMA), atomic force microscopy (AFM), thermal investigations, water uptake (WU) measurements, and ionic exchange capacity (IEC) tests have been used as characterization tools for the nanocomposite membranes. The nature of the tin oxide precursor, as well as the synthesis procedure, were found to play an important role in determining the morphology and the particle size distribution of the ceramic powder, this affecting the effective functionalization of the oxides. The incorporation of such particles, having sulphate groups on their surface, altered some peculiar properties of the resulting composite membrane, such as water content, thermo-mechanical, and morphological characteristics. PMID:24957125

  5. Ultra-thin Solid-State Li-Ion Electrolyte Membrane Facilitated by a Self-Healing Polymer Matrix.

    PubMed

    Whiteley, Justin M; Taynton, Philip; Zhang, Wei; Lee, Se-Hee

    2015-11-18

    Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes. PMID:26421754

  6. Interaction of gas molecules with crystalline polymer separation membranes: Atomic-scale modeling and first-principles calculations

    SciTech Connect

    Sergey N. Rashkeev; Eric S. Peterson

    2011-11-01

    Carbon dioxide (CO2)-induced plasticization can significantly decrease the gas separation performance of membranes in high-temperature or high pressure conditions, such as industrial methane (CH4) separations. In this paper, we investigated the crystalline phase of three polymers (polybenzimidazole (PBI), Bis(isobutylcarboxy)polybenzimidazole (PBI-Butyl), and KaptonTM) and interactions between gas molecules (CO2 and N2) and these polymers. A novel, molecular dynamics (MD) based, computational technique was employed to find unknown crystalline structures of these polymer materials. The interaction of CO2 and N2 gases with these crystals was studied by first-principles calculations and by classical MD simulations. The results showed that the packing structure and the interlayer coupling in polymer crystals determine the permeability and diffusivity of gas molecules. This methodology also allows prediction of plastic swelling in these materials caused by gas molecules absorbed in the polymer matrix.

  7. Morphological control of inter-penetrating polymer networks

    NASA Technical Reports Server (NTRS)

    Hansen, Marion

    1989-01-01

    Synthetic organic polymer chemistry has been successful in producing composition of matter with thermal oxidation stability and progressively higher glass transition temperatures. In part, this was done by increasing the steric-hindrance of moieties in the chain of a macromolecule. The resulting polymers are usually quite insoluble and produce molten polymers of very high viscosities. These types of polymers are not easily processed into graphite fiber prepregs by melt or solution impregnation methods. Hence, a technological need exists to produce new knowledge of how to produce polymer-fiber composites from this class of polymers. The concept of freeze drying amic-acid prepolymers with reactive thermoplastic was proposed as a research topic for the ASEE/NASA Summer Faculty Program of 1989 as a means of producing polymer-fiber composites. This process scheme has the thermodynamic attribute that the magnitude of phase separation due to differences in solubility of two organic constituents in solution will be greatly reduced by removing a solvent not by evaporation but by sublimation. Progress to date on evaluating this polymer processing concept is briefly outlined.

  8. Poly(cyclohexadiene)-Based Polymer Electrolyte Membranes for Fuel Cell Applications

    SciTech Connect

    Mays, Jimmy W.

    2011-03-07

    The goal of this research project was to create and develop fuel cell membranes having high proton conductivity at high temperatures and high chemical and mechanical durability. Poly(1,3-cyclohexadiene) (PCHD) is of interest as an alternative polymer electrolyte membrane (PEM) material due to its ring-like structure which is expected to impart superior mechanical and thermal properties, and due to the fact that PCHD can readily be incorporated into a range of homopolymer and copolymer structures. PCHD can be aromatized, sulfonated, or fluorinated, allowing for tuning of key performance structure and properties. These factors include good proton transport, hydrophilicity, permeability (including fuel gas impermeability), good mechanical properties, morphology, thermal stability, crystallinity, and cost. The basic building block, 1,3-cyclohexadiene, is a hydrocarbon monomer that could be inexpensively produced on a commercial scale (pricing typical of other hydrocarbon monomers). Optimal material properties will result in novel low cost PEM membranes engineered for high conductivity at elevated temperatures and low relative humidities, as well as good performance and durability. The primary objectives of this project were: (1) To design, synthesize and characterize new non-Nafion PEM materials that conduct protons at low (25-50%) RH and at temperatures ranging from room temperature to 120 C; and (2) To achieve these objectives, a range of homopolymer and copolymer materials incorporating poly(cyclohexadiene) (PCHD) will be synthesized, derivatized, and characterized. These two objectives have been achieved. Sulfonated and crosslinked PCHD homopolymer membranes exhibit proton conductivities similar to Nafion in the mid-RH range, are superior to Nafion at higher RH, but are poorer than Nafion at RH < 50%. Thus to further improve proton conductivity, particularly at low RH, poly(ethylene glycol) (PEG) was incorporated into the membrane by blending and by

  9. A mathematical model for predicting the life of polymer electrolyte fuel cell membranes subjected to hydration cycling

    NASA Astrophysics Data System (ADS)

    Burlatsky, S. F.; Gummalla, M.; O'Neill, J.; Atrazhev, V. V.; Varyukhin, A. N.; Dmitriev, D. V.; Erikhman, N. S.

    2012-10-01

    Under typical Polymer Electrolyte Membrane Fuel Cell (PEMFC) fuel cell operating conditions, part of the membrane electrode assembly is subjected to humidity cycling due to variation of inlet gas RH and/or flow rate. Cyclic membrane hydration/dehydration would cause cyclic swelling/shrinking of the unconstrained membrane. In a constrained membrane, it causes cyclic stress resulting in mechanical failure in the area adjacent to the gas inlet. A mathematical modeling framework for prediction of the lifetime of a PEMFC membrane subjected to hydration cycling is developed in this paper. The model predicts membrane lifetime as a function of RH cycling amplitude and membrane mechanical properties. The modeling framework consists of three model components: a fuel cell RH distribution model, a hydration/dehydration induced stress model that predicts stress distribution in the membrane, and a damage accrual model that predicts membrane lifetime. Short descriptions of the model components along with overall framework are presented in the paper. The model was used for lifetime prediction of a GORE-SELECT membrane.

  10. An all-aqueous route to polymer brush-modified membranes with remarkable permeabilites and protein capture rates

    PubMed Central

    Anuraj, Nishotha; Bhattacharjee, Somnath; Geiger, James H.; Baker, Gregory L.; Bruening, Merlin L.

    2011-01-01

    Microporous membranes are attractive for protein purification because convection rapidly brings proteins to binding sites. However, the low binding capacity of such membranes limits their applications. This work reports a rapid, aqueous procedure to create highly permeable, polymer brush-modified membranes that bind large amounts of protein. The synthetic method includes a 10-min adsorption of a macroinitiator in a hydroxylated nylon membrane and a subsequent 5-min aqueous atom transfer radical polymerization of 2-(methacryloyloxy)ethyl succinate from the immobilized initiator to form poly(acid) brushes. This procedure likely leads to more swollen, less dense brushes than polymerization from silane initiators, and thus requires less polymer to achieve the same binding capacity. The hydraulic permeability of the poly(acid) membranes is 4-fold higher than that of similar membranes prepared by growing brushes from immobilized silane initiators. These brush-containing nylon membranes bind 120 mg/cm3 of lysozyme using solution residence times as short as 35 ms, and when functionalized with nitrilotriacetate (NTA)-Ni2+ complexes, they capture 85 mg/cm3 of histidine6-tagged (His-tagged) Ubiquitin. Additionally the NTA-Ni2+-functionalized membranes isolate His-tagged myo-inositol-1-phosphate synthase directly from cell extracts and show >90% recovery of His-tagged proteins. PMID:22287817

  11. Hole size distributions in cardo-based polymer membranes deduced from the lifetimes of ortho-positronium

    NASA Astrophysics Data System (ADS)

    Kobayashi, Y.; Kinomura, A.; Kazama, S.; Inoue, K.; Toyama, T.; Nagai, Y.; Haraya, K.; Mohamed, H. F. M.; O'Rourke, B. E.; Oshima, N.; Suzuki, R.

    2016-01-01

    To clarify the free volume size distributions of the cardo-based polymer membranes, where ortho-positronium (o-Ps) undergoes pick-off annihilation, the o-Ps lifetime distributions were analyzed by the LT9 programme. It was found that the cardo-based polysulfone membrane has much narrower o-Ps lifetime/hole size distributions than the cardo-based polyimide membranes with the 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) moiety. Further, the lifetime/hole size distributions of the cardo-based polymer membranes are appreciably broadened with increasing temperature. This suggests that in these membranes there are holes not only of different sizes but also of different thermal expansion coefficients. It is also shown that in a membrane with a wider hole size distribution the average o-Ps lifetime tends to be longer than would be expected from the correlation between the o-Ps lifetime and the total free volume for common polymers.

  12. Network pattern of residue packing in helical membrane proteins and its application in membrane protein structure prediction.

    PubMed

    Pabuwal, Vagmita; Li, Zhijun

    2008-01-01

    De novo protein structure prediction plays an important role in studies of helical membrane proteins as well as structure-based drug design efforts. Developing an accurate scoring function for protein structure discrimination and validation remains a current challenge. Network approaches based on overall network patterns of residue packing have proven useful in soluble protein structure discrimination. It is thus of interest to apply similar approaches to the studies of residue packing in membrane proteins. In this work, we first carried out such analysis on a set of diverse, non-redundant and high-resolution membrane protein structures. Next, we applied the same approach to three test sets. The first set includes nine structures of membrane proteins with the resolution worse than 2.5 A; the other two sets include a total of 101 G-protein coupled receptor models, constructed using either de novo or homology modeling techniques. Results of analyses indicate the two criteria derived from studying high-resolution membrane protein structures are good indicators of a high-quality native fold and the approach is very effective for discriminating native membrane protein folds from less-native ones. These findings should be of help for the investigation of the fundamental problem of membrane protein structure prediction. PMID:18178566

  13. Perfluorocyclobutyl polymer thin-film composite membrane fabrication, plasticization and physical aging

    NASA Astrophysics Data System (ADS)

    Zhou, Jinxiang

    My research consists of three parts: 1) study of perfluorocyclobutyl (PFCB) thin film formation, 2) development and characterization of PFCB thin-film composite membranes, and 3) elucidation of the roles that plasticization and physical aging play on PFCB thin-film performance. In part 1, I conducted comprehensive research to understand how PFCB thin films form by the method of dip coating. Through the control of solvents, polymer solution concentrations, and withdrawal speeds, a series of PFCB thin films were formed on silicon wafers. Film thickness and refractive index were characterized by ellipsometry. Results suggested that when the withdrawal speeds are higher than 50 mm/min, film thickness increases with increasing withdrawal speeds, as it is predicted in the proposed extension of the Landau-Levich model. When the withdrawal speeds are lower than 50 mm/min, film thickness increases with decreasing withdrawal speeds, which could be explained by the phenomenon of PFCB surface excess. Subsequent surface tension studies proved the existence of this surface excess. Surface images of these films were measured by atomic force microscope. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. Based on the knowledge generated in part 1, I developed, from scratch, procedures to prepare PFCB TFC membranes that were free of major defects. I used mathematical models based on resistance in series to predict composite membrane performance. In many cases, surface defects are the major reason for poor separation ability of TFC membranes. Mathematical analysis showed that the surface defects are less critical in thinner films but are still an important factor causing selectivity loss. Surface defects occur mainly from polymer dewetting on the

  14. Structural and ionic conductivity studies of electrospun polymer blend P(VdF-co-HFP)/PMMA electrolyte membrane for lithium battery application

    SciTech Connect

    Padmaraj, O.; Satyanarayana, N.; Venkateswarlu, M.

    2015-06-24

    A novel fibrous polymer blend [(100-x) % P(VdF-co-HFP)/x % PMMA, x = 10, 20, 30, 40, 50] electrolyte membranes were prepared by electrospinning technique. Structural, thermal and surface morphology of all the compositions of electrospun polymer blend membranes were studied by using XRD, DSC & SEM. The newly developed five different compositions of polymer blend fibrous electrolyte membranes were obtained by soaking in an electrolyte solution contains 1M LiPF{sub 6} in EC: DEC (1:1,v/v). The wet-ability and conductivity of all the compositions of polymer blend electrolyte membranes are evaluated through electrolyte uptake and impedance measurements. The polymer blend [90% P(VdF-co-HFP)/10% PMMA] electrolyte membrane showed good wet-ability and high conductivity (1.788 × 10{sup −3} Scm{sup −1}) at room temperature.

  15. A supramolecular cross-linked conjugated polymer network for multiple fluorescent sensing.

    PubMed

    Ji, Xiaofan; Yao, Yong; Li, Jinying; Yan, Xuzhou; Huang, Feihe

    2013-01-01

    A supramolecular cross-linked network was fabricated and demonstrated to act as a multiple fluorescent sensor. It was constructed from a fluorescent conjugated polymer and a bisammonium salt cross-linker driven by dibenzo[24]crown-8/secondary ammonium salt host-guest interactions. Compared with the conjugated polymer, the network has weak fluorescence due to the aggregation of polymer chains. Thanks to the multiple stimuli-responsiveness of host-guest interactions, the fluorescence intensity of the system can be enhanced by four types of signals, including potassium cation, chloride anion, pH increase, and heating. Hence, the network can serve as a cation sensor, an anion sensor, a pH sensor, and a temperature sensor. It can be used in both solution and thin film. Interestingly, exposure of a film made from this supramolecular cross-linked network to ammonia leads to an increase of fluorescence, making it a good candidate for gas detection. PMID:23259828

  16. Chemorheology of phenylboronate-salicylhydroxamate crosslinked hydrogel networks with a sulfonated polymer backbone

    PubMed Central

    Roberts, Meredith C.; Mahalingam, Alamelu; Hanson, Melissa C.; Kiser, Patrick F.

    2012-01-01

    Hydrogel networks crosslinked with polymer-bound phenylboronic acid (PBA) and salicylhydroxamic acid (SHA) demonstrate pH-reversible gel behavior due to the pH-dependent equilibrium of the crosslinking moieties that form the gel network. Furthermore, the pH at which gels behave dynamically can be controlled by use of a polyelectrolyte backbone. Here we report on the frequency-dependent chemorheological characterization of PBA-SHA crosslinked hydrogel networks with a sulfonated polymer backbone. Our results suggest that the anionic nature of the polymers allows reversible crosslinking at neutral pH that an otherwise neutral-backboned PBA-SHA crosslinked network cannot, and that these charge-induced dynamics can be effectively screened by ions in solution. Moreover, moduli-frequency data can effectively be reduced into a single master curve with a neutral-backboned PBA-SHA gel data set as the reference condition. PMID:23132956

  17. Preparation and characterization of light-switchable polymer networks attached to solid substrates.

    PubMed

    Schenderlein, Helge; Voss, Agnieszka; Stark, Robert W; Biesalski, Markus

    2013-04-01

    Surface-attached polymer networks that carry light-responsive nitrospiropyran groups in a hydrophilic PDMAA matrix were prepared on planar silicon and glass surfaces and were characterized with respect to their switching behavior under the influence of an external light trigger. Functional polymers bearing light-responsive units as well as photo-cross-linkable benzophenone groups were first synthesized using free radical copolymerization. The number of spiropyran groups in the copolymer was controlled by adjusting the concentration of the respective monomer in the copolymerization feed. The polymer films were prepared by spin-coating the functional polymers from solution and by ultraviolet light (UV)-induced cross-linking utilizing benzophenone photochemistry. On substrates with immobilized benzophenone groups, the complete polymer network is linked to the surface. The dry thickness of the films can be controlled over a wide range from a few nanometers up to more than 1 μm. The integration of such light-switchable organic moieties into a surface-attached polymer network allows one to increase the overall number of light-responsive groups per surface area by adjusting the amount of surface-attached polymer networks. The spiropyran's function in dry (solvent-free) and swollen polymer films can be reversibly switched by UV and visible irradiation. In addition, the switching in water is faster than in the dry state. Therefore, implementing light-responsive spiropyran functions in polymer films linked to solid surfaces could allow for switching of the chemical and optical surface properties in a fast and spatially controlled fashion. PMID:23461870

  18. A theory for species migration in a finitely strained solid with application to polymer network swelling

    NASA Astrophysics Data System (ADS)

    Duda, Fernando P.; Souza, Angela C.; Fried, Eliot

    2010-04-01

    We present a theory for the behavior of a solid undergoing two interdependent processes, a macroscopic or mechanical process due to the deformation of the solid and a microscopic or chemical process due to the migration of a chemical species through the solid. The principle of virtual power is invoked to deduce the basic balances of the theory, namely the mechanical force balance and the transport balance for the chemical species. In combination with thermodynamically consistent constitutive relations, these balances generate the basic equations of the theory. Keeping in mind applications involving the swelling of polymer networks by liquids, a specialization of the theory is presented and applied to study the influences of mechanical and chemical interactions on equilibrium states and diffusive dynamical processes. It is shown that the possibility of a mechanically induced phase transition is governed by two parameters: the Flory interaction parameter and a parameter given by the product between the number of cross-linked units per unit reference volume and the molecular volume of the liquid molecule. As for diffusion, it is shown that the theory is able to describe the pressure-induced diffusion in swollen membranes.

  19. Sensor-actuator coupled device for active tracheal tube using solid polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    Ihara, Tadashi; Nakamura, Taro; Mukai, Toshiharu; Asaka, Kinji

    2007-04-01

    A sensor-actuator coupled device was developed using solid polymer electrolyte membrane (SPM) as an active tracheal tube for ventilator. Active tracheal tube is a novel type of tube for ventilator that removes patient's phlegm automatically upon sensing the narrowing of trachea by phlegm. This type of active tube is extremely useful in clinical settings as currently the sole measure to remove phlegm from patient's tube is to do it manually by a nurse every few hours. As SPM works both as a sensor and an actuator, an effective compact device was developed. SPM based sensor-actuator coupled device was fabricated with modified gold plating method. Prepared SPM was fixed as an array on a plastic pipe of diameter 22 mm and was connected to a ventilator circuit and driven by a ventilator with a volume control ventilation (VCV) mode. SPM was connected both to a sensing unit and an actuation unit. Generated voltage developed by the membrane with the setting of the maximum pressure from 5 cmH IIO to 20 cmH IIO was in order of several hundred μV. SPM sensor demonstrated a biphasic response to the ventilator flow. The sensor data showed nearly linearly proportional voltage development to the intra-tracheal pressure. The sensed signal was filtered and digitized with an A/D converting unit on a PC board. A real time operating program was used to detect the sensed signal that indicates the narrowing of trachea. The program then activated a driving signal to control the actuation of the membrane. The signal was sent to a D/A converting unit. The output of the D/A unit was sent to an amplifier and the galvanostat unit which drives the membrane with constant current regardless of the change in the load. It was demonstrated that the sensor-actuator unit detects the narrowing of trachea within several hundreds milli-seconds and responds by actuating the same membrane with the driving voltage of 3-4 V and driving current of several hundred milli-ampere for each membrane. SPM array

  20. Positron trapping and possible presence of SO3H clusters in dry fluorinated polymer electrolyte membranes

    NASA Astrophysics Data System (ADS)

    Mohamed, Hamdy F. M.; Kobayashi, Y.; Kuroda, S.; Ohira, A.

    2012-08-01

    The behavior of positrons that do not form positronium in dry fluorinated polymer electrolyte membranes (Nafion®, Fumapem® and Aquivion®) with various ion exchange capacities (IECs) was studied by the combined use of Doppler broadening of annihilation radiation (DBAR) and the positron lifetime technique. The drastic increase of the S parameter, measured by DBAR, with increasing IEC above 0.91 meq/g indicates that increasing numbers of positrons are trapped by oxygen atoms and annihilate with the electrons bound in them. Reversed micelle like SO3H nanoclusters to trap positrons possibly appear at IEC = 0.91 meq/g and their concentration increases with increasing IEC.

  1. Performance of laboratory polymer electrolyte membrane hydrogen generator with sputtered iridium oxide anode

    NASA Astrophysics Data System (ADS)

    Labou, D.; Slavcheva, E.; Schnakenberg, U.; Neophytides, S.

    The continuous improvement of the anode materials constitutes a major challenge for the future commercial use of polymer electrolyte membranes (PEM) electrolyzers for hydrogen production. In accordance to this direction, iridium/titanium films deposited directly on carbon substrates via magnetron sputtering are operated as electrodes for the oxygen evolution reaction interfaced with Nafion 115 electrolyte in a laboratory single cell PEM hydrogen generator. The anode with 0.2 mg cm -2 Ir catalyst loading was electrochemically activated by cycling its potential value between 0 and 1.2 V (vs. RHE). The water electrolysis cell was operated at 90 °C with current density 1 A cm -2 at 1.51 V without the ohmic contribution. The corresponding current density per mgr of Ir catalyst is 5 A mg -1. The achieved high efficiency is combined with sufficient electrode stability since the oxidation of the carbon substrate during the anodic polarization is almost negligible.

  2. Metallic plate corrosion and uptake of corrosion products by nafion in polymer electrolyte membrane fuel cells.

    PubMed

    Bozzini, Benedetto; Gianoncelli, Alessandra; Kaulich, Burkhard; Kiskinova, Maya; Prasciolu, Mauro; Sgura, Ivonne

    2010-07-19

    Nafion contamination by ferrous-alloy corrosion products, resulting in dramatic drops of the Ohmic potential, is a suspected major failure mode of polymer electrolyte membrane fuel cells that make use of metallic bipolar plates. This study demonstrates the potential of scanning transmission X-ray microscopy combined with X-ray absorption and fluorescence microspectroscopy for exploring corrosion processes of Ni and Fe electrodes in contact with a hydrated Nafion film in a thin-layer cell. The imaged morphology changes of the Ni and Fe electrodes and surrounding Nafion film that result from relevant electrochemical processes are correlated to the spatial distribution, local concentration, and chemical state of Fe and Ni species. The X-ray fluorescence maps and absorption spectra, sampled at different locations, show diffusion of corrosion products within the Nafion film only in the case of the Fe electrodes, whereas the Ni electrodes appear corrosion resistant. PMID:20564283

  3. A multiple-responsive self-healing supramolecular polymer gel network based on multiple orthogonal interactions.

    PubMed

    Zhan, Jiayi; Zhang, Mingming; Zhou, Mi; Liu, Bin; Chen, Dong; Liu, Yuanyuan; Chen, Qianqian; Qiu, Huayu; Yin, Shouchun

    2014-08-01

    Supramolecular polymer networks have attracted considerable attention not only due to their topological importance but also because they can show some fantastic properties such as stimuli-responsiveness and self-healing. Although various supramolecular networks are constructed by supramolecular chemists based on different non-covalent interactions, supramolecular polymer networks based on multiple orthogonal interactions are still rare. Here, a supramolecular polymer network is presented on the basis of the host-guest interactions between dibenzo-24-crown-8 (DB24C8) and dibenzylammonium salts (DBAS), the metal-ligand coordination interactions between terpyridine and Zn(OTf)2 , and between 1,2,3-triazole and PdCl2 (PhCN)2 . The topology of the networks can be easily tuned from monomer to main-chain supramolecular polymer and then to the supramolecular networks. This process is well studied by various characterization methods such as (1) H NMR, UV-vis, DOSY, viscosity, and rheological measurements. More importantly, a supramolecular gel is obtained at high concentrations of the supramolecular networks, which demonstrates both stimuli-responsiveness and self-healing properties. PMID:24943122

  4. The Chemical Behavior and Degradation Mitigation Effect of Cerium Oxide Nanoparticles in Perfluorosulfonic Acid Polymer Electrolyte Membranes

    SciTech Connect

    Pearman, Benjamin P; Mohajeri, Nahid; Slattery, Darlene; Hampton, Michael; Seal, Sudipta; Cullen, David A

    2013-01-01

    Perfluorosulfonic acid membranes, the polymer of choice for polymer electrolyte hydrogen fuel cells, are susceptible to degradation due to attacks on polymer chains from radicals. Mitigation of this attack by cerium-based radical scavengers is an approach that has shown promise. In this work, two formulations of single-crystal cerium oxide nanoparticles, with an order of magnitude difference in particle size, are incorporated into said membranes and subjected to proton conductivity measurements and ex-situ durability tests. We found that ceria is reduced to Ce(III) ions in the acidic environment of a heated, humidified membrane which negatively impacts proton conductivity. In liquid and gas Fenton testing, fluoride emission is reduced by an order of magnitude, drastically increasing membrane longevity. Side-product analysis demonstrated that in the liquid Fenton test, the main point of attack are weak polymer end groups, while in the gas Fenton test, there is additional side-chain attack. Both mechanisms are mitigated by the addition of the ceria nanoparticles, whereby the extent of the durability improvement is found to be independent of particle size.

  5. Analysis of Tubular Membrane Networks in Cardiac Myocytes from Atria and Ventricles

    PubMed Central

    Kohl, Tobias; Lehnart, Stephan E.

    2014-01-01

    In cardiac myocytes a complex network of membrane tubules - the transverse-axial tubule system (TATS) - controls deep intracellular signaling functions. While the outer surface membrane and associated TATS membrane components appear to be continuous, there are substantial differences in lipid and protein content. In ventricular myocytes (VMs), certain TATS components are highly abundant contributing to rectilinear tubule networks and regular branching 3D architectures. It is thought that peripheral TATS components propagate action potentials from the cell surface to thousands of remote intracellular sarcoendoplasmic reticulum (SER) membrane contact domains, thereby activating intracellular Ca2+ release units (CRUs). In contrast to VMs, the organization and functional role of TATS membranes in atrial myocytes (AMs) is significantly different and much less understood. Taken together, quantitative structural characterization of TATS membrane networks in healthy and diseased myocytes is an essential prerequisite towards better understanding of functional plasticity and pathophysiological reorganization. Here, we present a strategic combination of protocols for direct quantitative analysis of TATS membrane networks in living VMs and AMs. For this, we accompany primary cell isolations of mouse VMs and/or AMs with critical quality control steps and direct membrane staining protocols for fluorescence imaging of TATS membranes. Using an optimized workflow for confocal or superresolution TATS image processing, binarized and skeletonized data are generated for quantitative analysis of the TATS network and its components. Unlike previously published indirect regional aggregate image analysis strategies, our protocols enable direct characterization of specific components and derive complex physiological properties of TATS membrane networks in living myocytes with high throughput and open access software tools. In summary, the combined protocol strategy can be readily applied

  6. Thermally cured semi-interpenetrating electrolyte networks (s-IPN) for safe and aging-resistant secondary lithium polymer batteries

    NASA Astrophysics Data System (ADS)

    Nair, Jijeesh R.; Destro, Matteo; Bella, Federico; Appetecchi, Giovanni B.; Gerbaldi, Claudio

    2016-02-01

    Truly solid polymer electrolyte membranes are designed by thermally induced free radical polymerisation. The overall membrane architecture is built on a semi-interpenetrating polymer network (s-IPN) structure, where a di-methacrylate oligomer is cross-linked (in situ) in the presence of a long thermoplastic linear PEO chain and a supporting lithium salt to obtain a freestanding, flexible and non-tacky film. In the envisaged systems, the di-methacrylate functions as a soft cross-linker, thus avoiding physico-mechanical deformation of the s-IPNs at elevated temperature, without hampering the ionic conductivity. s-IPNs exhibit remarkable stability towards lithium metal and no traces of impurity are detected while testing their oxidation stability (4.7 V vs. Li/Li+) towards anodic potential. The newly elaborated system is also successfully tested at moderately high temperature in Li metal cells in which LiFePO4/C is used as the cathode active material, showing excellent indications of safe and highly durable electrolyte separator (i.e., 2000 cycles at reasonably high 1C rate).

  7. Permethyl Cobaltocenium (Cp*2Co+) as an Ultra-Stable Cation for Polymer Hydroxide-Exchange Membranes

    PubMed Central

    Gu, Shuang; Wang, Junhua; Kaspar, Robert B.; Fang, Qianrong; Zhang, Bingzi; Bryan Coughlin, E.; Yan, Yushan

    2015-01-01

    Hydroxide (OH−)-exchange membranes (HEMs) are important polymer electrolytes enabling the use of affordable and earth-abundant electrocatalysts for electrochemical energy-conversion devices such as HEM fuel cells, HEM electrolyzers, and HEM solar hydrogen generators. Many HEM cations exist, featuring desirable properties, but new cations are still needed to increase chemical stability at elevated temperatures. Here we introduce the permethyl cobaltocenium [(C5Me5)2Co(III)+ or Cp*2Co+] as an ultra-stable organic cation for polymer HEMs. Compared with the parent cobaltocenium [(C5H5)2Co(III)+ or Cp2Co+], Cp*2Co+ has substantially higher stability and basicity. With polysulfone as an example, we demonstrated the feasibility of covalently linking Cp*2Co+ cation to polymer backbone and prepared Cp*2Co+-functionalized membranes as well. The new cation may be useful in designing more durable HEM electrochemical devices. PMID:26119573

  8. Permethyl Cobaltocenium (Cp*2Co+) as an Ultra-Stable Cation for Polymer Hydroxide-Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Gu, Shuang; Wang, Junhua; Kaspar, Robert B.; Fang, Qianrong; Zhang, Bingzi; Bryan Coughlin, E.; Yan, Yushan

    2015-06-01

    Hydroxide (OH-)-exchange membranes (HEMs) are important polymer electrolytes enabling the use of affordable and earth-abundant electrocatalysts for electrochemical energy-conversion devices such as HEM fuel cells, HEM electrolyzers, and HEM solar hydrogen generators. Many HEM cations exist, featuring desirable properties, but new cations are still needed to increase chemical stability at elevated temperatures. Here we introduce the permethyl cobaltocenium [(C5Me5)2Co(III)+ or Cp*2Co+] as an ultra-stable organic cation for polymer HEMs. Compared with the parent cobaltocenium [(C5H5)2Co(III)+ or Cp2Co+], Cp*2Co+ has substantially higher stability and basicity. With polysulfone as an example, we demonstrated the feasibility of covalently linking Cp*2Co+ cation to polymer backbone and prepared Cp*2Co+-functionalized membranes as well. The new cation may be useful in designing more durable HEM electrochemical devices.

  9. Voltage tuning of the resonance frequency of electroactive polymer membranes over a range of more than 75%

    NASA Astrophysics Data System (ADS)

    Dubois, Philippe; Rosset, Samuel; Niklaus, Muhamed; Shea, Herbert

    2009-05-01

    We report on a novel technique to control the resonance frequency of polymer membranes, without additional external actuators. An electrostatic force is used to apply compressive stress to a dielectric electroactive polymers membrane, consisting of a 25 micron thick, 1 to 4 mm diameter, polydimethylsiloxane (PDMS) film bonded onto patterned silicon or Pyrex wafers. Both sides of the membranes are rendered conductive by low-energy metal ion implantation. Ion implantation is chosen because it stiffens the membrane much less than sputtering a film of similar thickness [1][2]. The initial resonance frequency of the membrane is given by its geometry, the Young's modulus and stress of the composite film. The technique presented here allows tuning the resonance frequency from this initial value down to zero (at the buckling threshold) by adding compressive stress due to a voltage difference applied to the electrodes on both sides of the membrane. We have measured a reduction of the first mode resonance frequency of up to 77% (limited by dielectric breakdown) for ion-implanted membranes [3]. The tuning is repeatable and allows for continuous variation. Excellent agreement was found between our measurements and an analytical model we developed based on the Rayleigh-Ritz theory.

  10. Polymer dynamics of DOC networks and gel formation in seawater

    NASA Astrophysics Data System (ADS)

    Verdugo, Pedro; Santschi, Peter H.

    2010-08-01

    scale, where the assignment of static bulk features including dimension, concentration, functionalities and vertical fluxes can be open to question. This brief revision illustrates two case studies that show how simple methods and principles of polymer networks theory can be used to advance the understanding of one of the most intriguing and significant processes taking place in the ocean. Namely, the kinetics and thermodynamics of: (a) Ca-driven DOC self-assembly, and (b) hydrophobic bond-driven self assembly of DOC by amphiphilic exopolymers released by marine bacteria.

  11. Amphiphilic semi-interpenetrating polymer networks using pulverized rubber

    NASA Astrophysics Data System (ADS)

    Shahidi, Nima

    Scrap rubber materials provide a significant challenge to either reuse or safe disposal. Every year, millions of tires are discarded to landfills in the United States, consuming a staggering amount of land space, creating a high risk for large fires, breeding mosquitoes that spread diseases, and wasting the planet's natural resources. This situation cannot be sustained. The challenge of reusing scrap rubber materials is mainly due to the crosslinked structure of vulcanized rubber that prevent them from melting and further processing for reuse. The most feasible recycling approach is believed to be a process in which the vulcanized rubber is first pulverized into a fine powder and then incorporated into new products. The production of fine rubber particles is generally accomplished through the use of a cryogenic process that is costly. Therefore, development of a cost effective technology that utilizes a large quantity of the scrap rubber materials to produce high value added materials is an essential element in maintaining a sustainable solution to rubber recycling. In this research, a cost effective pulverization process, solid state shear extrusion (SSSE), was modified and used for continuous pulverization of the rubber into fine particles. In the modified SSSE process, pulverization takes place at high compressive shear forces and a controlled temperature. Furthermore, an innovative particle modification process was developed to enhance the chemical structure and surface properties of the rubber particles for manufacturing of high value added products. Modification of rubber particles was accomplished through the polymerization of a hydrophilic monomer mixture within the intermolecular structure of the hydrophobic rubber particles. The resulting composite particles are considered as amphiphilic particulate phase semi-interpenetrating polymer networks (PPSIPNs). The modified rubber particles are water dispersible and suitable for use in a variety of aqueous media

  12. Recyclable Crosslinked Polymer Networks via One-Step Controlled Radical Polymerization.

    PubMed

    Jin, Kailong; Li, Lingqiao; Torkelson, John M

    2016-08-01

    A nitroxide-mediated polymerization strategy allows one-step synthesis of recyclable crosslinked polymeric materials from any monomers or polymers that contain carbon-carbon double bonds amenable to radical polymerization. The resulting materials with dynamic covalent bonds can show full property recovery after multiple melt-reprocessing recycles. This one-step strategy provides for both robust, relatively sustainable recyclability of crosslinked polymers and design of networks for advanced technologies. PMID:27206061

  13. Physical Property Requirements of Ion-exchange Polymer Membranes for Acid-base Flow Batteries

    NASA Astrophysics Data System (ADS)

    Roddecha, Supacharee; Thayer, Peter; Jorne', Jacob; Anthamatten, Mitchell

    2013-03-01

    Flow batteries offer feasible solutions to grid-scale storage of intermittent power. We are developing a new type of flow battery that reversibly controls an acid-base neutralization reaction. The battery consists of two highly reversible hydrogen gas electrodes that are exposed to low and high pH process streams. A brine solution runs between the acid and base streams and is separated by cationic and anionic exchange membranes. For both charge and discharge phases, hydrogen gas is produced at one electrode and consumed at the other. During charging, an external potential is applied across the two electrodes to electrochemically produce acid and base from the fed brine solution. Discharge involves electrochemical neutralization of acid and base streams, resulting in current flow through an external load. Several charge and discharge cycles were performed to demonstrate proof of concept. Experiments were conducted to determine the physical property requirements of the ionic exchange polymer layers. Properties including ion conductivity, permselectivity, and membrane stability will be discussed.

  14. Systematic approach to development of pressure sensors using dielectric electro-active polymer membranes

    NASA Astrophysics Data System (ADS)

    York, A.; Dunn, J.; Seelecke, S.

    2013-09-01

    Dielectric electro-active polymers (DEAPs) have become attractive materials for various actuation and sensing applications due to their high energy and power density, high efficiency, light weight, and fast response speed. However, commercial development has been hindered due to a variety of constraints such as reliability, non-linear behavior, cost of driving electronics, and form factor requirements. This paper presents the systematic development from laboratory concept to commercial readiness of a novel pressure sensing system using a DEAP membrane. The pressure sensing system was designed for in-line pressure measurements for low pressure applications such as health systems monitoring. A first generation sensor was designed, built and tested with a focus on the qualitative capabilities of EAP membranes as sensors. Experimental measurements were conducted that demonstrated the capability of the sensor to output a voltage signal proportional to a changing pressure. Several undesirable characteristics were observed during these initial tests such as strong hysteresis, non-linearity, very limited pressure range, and low fatigue life. A second generation prototype was then designed to remove or compensate for these undesirable characteristics. This prototype was then built and tested. The new design showed an almost complete removal of hysteretic non-linear effects and was capable of operating at 10 × the pressure range of the initial generation. This new design is the framework for a novel DEAP based pressure sensor ready for commercial applications.

  15. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  16. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  17. Ab initio molecular dynamics simulation of proton hopping in a model polymer membrane.

    PubMed

    Devanathan, Ram; Idupulapati, Nagesh; Baer, Marcel D; Mundy, Christopher J; Dupuis, Michel

    2013-12-27

    We report the results of ab initio molecular dynamics simulations of a model Nafion polymer membrane initially equilibrated using classical molecular dynamics simulations. We studied three hydration levels (λ) of 3, 9, and 15 H2O/SO3(-) corresponding to dry, hydrated, and saturated fuel cell membrane, respectively. The barrier for proton transfer from the SO3(-)-H3O(+) contact ion pair to a solvent-separated ion pair decreased from 2.3 kcal/mol for λ = 3 to 0.8 kcal/mol for λ = 15. The barrier for proton transfer between two water molecules was in the range from 0.7 to 0.8 kcal/mol for the λ values studied. The number of proton shuttling events between a pair of water molecules is an order of magnitude more than the number of proton hops across three distinct water molecules. The proton diffusion coefficient at λ = 15 is about 0.9 × 10(-5) cm(2)/s, which is in good agreement with experiment and our previous quantum hopping molecular dynamics simulations. PMID:24320080

  18. Polymer electrolyte membrane fuel cell performance degradation by coolant leakage and recovery

    NASA Astrophysics Data System (ADS)

    Jung, Ju Hae; Kim, Se Hoon; Hur, Seung Hyun; Joo, Sang Hoon; Choi, Won Mook; Kim, Junbom

    2013-03-01

    Coolant leakage leads to decrease in performance during the operation of electric vehicles which make use of polymer electrolyte membrane fuel cells (PEMFC). This study examines the effects of various coolant leak conditions in 3-cell stack and single cell. The experimental results show that an irreversible reduction in performance occurs after coolant injection into the anode side of the stack. Poisoning of carbon monoxide (CO) on the platinum (Pt) catalyst is caused by electro-oxidation reaction of EG. Water cleaning is selected because CO poisoning is desorbed to reaction with water molecules. Performance is quickly reduced when the interval between coolant injections is short. Performance reduction is indicated by the experimental results for the gas diffusion layer (GDL) and the membrane electrode assembly (MEA). It shows that performance of the MEA with the GDL exposed to coolant decreased, but it is recovered after water cleaning. In contrast, results for performance of the MEA exposed to coolant for long time could not be reversed after water cleaning. Therefore, we propose that performance degradation of coolant leak on the Pt catalyst surface and GDL can be recovered by the water cleaning simply without disassembly of stack.

  19. Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

    NASA Astrophysics Data System (ADS)

    Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

    2014-08-01

    High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

  20. Enhanced stability of multilayer graphene-supported catalysts for polymer electrolyte membrane fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Marinkas, A.; Hempelmann, R.; Heinzel, A.; Peinecke, V.; Radev, I.; Natter, H.

    2015-11-01

    One of the biggest challenges in the field of polymer electrolyte membrane fuel cells (PEMFC) is to enhance the lifetime and the long-term stability of PEMFC electrodes, especially of cathodes, furthermore, to reduce their platinum loading, which could lead to a cost reduction for efficient PEMFCs. These demands could be achieved with a new catalyst support architecture consisting of a composite of carbon structures with significant different morphologies. A highly porous cathode catalyst support layer is prepared by addition of various carbon types (carbon black particles, multi-walled carbon nanotubes (MWCNT)) to multilayer graphene (MLG). The reported optimized cathodes shows extremely high durability and similar performance to commercial standard cathodes but with 89% lower Pt loading. The accelerated aging protocol (AAP) on the membrane electrode assemblies (MEA) shows that the presence of MLG increases drastically the durability and the Pt-extended electrochemical surface area (ECSA). In fact, after the AAP slightly enhanced performance can be observed for the MLG-containing cathodes instead of a performance loss, which is typical for the commercial carbon-based cathodes. Furthermore, the presence of MLG drastically decreases the ECSA loss rate. The MLG-containing cathodes show up to 6.8 times higher mass-normalized Pt-extended ECSA compared to the commercial standard systems.

  1. Performance prediction of circular dielectric electro-active polymers membrane actuators with various geometries

    NASA Astrophysics Data System (ADS)

    Hau, Steffen; York, Alexander; Seelecke, Stefan

    2015-04-01

    Circular dielectric electro-active polymer (DEAP) membrane actuators are easy to manufacture and therefore can be uniquely designed to perform optimally for specific applications. The performance of these actuators is naturally dependent on the materials used, and also dictated by the specific geometry of the circular design. For a given overall actuator size, changing their internal geometry will directly change the force and stroke output. In addition the DEAP technology itself is a promising technology for constructing lightweight, cost and energy efficient sensor and actuator systems. Thus, several potential applications like pressure sensors, pumps, valves, micro-positioners and loudspeakers were already proposed. The circular DEAP membrane actuators used in this study consist of a silicone based elastomer, carbon ink based electrodes, and are held together with a stiff frame. Experimentally collected force-displacement curves for these actuators can be used to determine force and stroke output of the actuators as described by Hodgins et al. in. This work presents an efficient method to predict these force-displacement plots and thus stroke and force output for different actuator geometries. These results than can be used to adapt the actuator geometry to the needs of a specific application with its particular force and stroke requirements. The prediction method is based on an average stress-stretch calculation for training samples. The calculated stress-stretch data is then geometry independent and can be used to predict desired geometry dependent force-displacement data for stroke and force output analysis.

  2. Binderless electrodes for high-temperature polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Martin, S.; Li, Q.; Steenberg, T.; Jensen, J. O.

    2014-12-01

    A new electrode concept was proved with no polymeric binder in the catalyst layer for acid-doped polybenzimidazole (PBI) membrane fuel cells. It shows that a stable interface between the membrane and the catalyst layer can be retained when a proton conducting acid phase is established. The absence of the polymer in the catalytic layer turned out to be beneficial for the PBI cell performance particularly under high load operation. The influence on performance of the Pt loading of the cathode was studied in a range from 0.11 to 2.04 mgPt cm-2 showing saturation of the maximum performance for Pt loadings higher than 0.5 mgPt cm-2. For fuel cell operation on H2 and air supplied under ambient pressure, a peak power density as high as 471 mW cm-2 was measured. The tolerance to carbon monoxide (CO) was also studied with Pt loadings of the anode ranging from 0.24 to 1.82 mgPt cm-2. Lifetime test for a MEA loaded with 0.96 mgPt cm-2 on both electrodes revealed no voltage decay during 900 h of uninterrupted operation at 200 mA cm-2 and 160 °C.

  3. Current collector design for closed-plenum polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Daniels, F. A.; Attingre, C.; Kucernak, A. R.; Brett, D. J. L.

    2014-03-01

    This work presents a non-isothermal, single-phase, three-dimensional model of the effects of current collector geometry in a 5 cm2 closed-plenum polymer electrolyte membrane (PEM) fuel cell constructed using printed circuit boards (PCBs). Two geometries were considered in this study: parallel slot and circular hole designs. A computational fluid dynamics (CFD) package was used to account for species, momentum, charge and membrane water distribution within the cell for each design. The model shows that the cell can reach high current densities in the range of 0.8 A cm-2-1.2 A cm-2 at 0.45 V for both designs. The results indicate that the transport phenomena are significantly governed by the flow field plate design. A sensitivity analysis on the channel opening ratio shows that the parallel slot design with a 50% opening ratio shows the most promising performance due to better species, heat and charge distribution. Modelling and experimental analysis confirm that flooding inhibits performance, but the risk can be minimised by reducing the relative humidity of the cathode feed to 50%. Moreover, overheating is a potential problem due to the insulating effect of the PCB base layer and as such strategies should be implemented to combat its adverse effects.

  4. Development of a polymer electrolyte membrane fuel cell stack for an underwater vehicle

    NASA Astrophysics Data System (ADS)

    Han, In-Su; Kho, Back-Kyun; Cho, Sungbaek

    2016-02-01

    This paper presents a polymer electrolyte membrane (PEM) fuel cell stack that is specifically designed for the propulsion of an underwater vehicle (UV). The stack for a UV must be continuously operated in a closed space using hydrogen and pure oxygen; it should meet various performance requirements such as high hydrogen and oxygen utilizations, low hydrogen and oxygen consumptions, a high ramp-up rate, and a long lifetime. To this end, a cascade-type stack design is employed and the cell components, including the membrane electrode assembly and bipolar plate, are evaluated using long-term performance tests. The feasibility of a fabricated 4-kW-class stack was confirmed through various performance evaluations. The proposed cascade-type stack exhibited a high efficiency of 65% and high hydrogen and oxygen utilizations of 99.89% and 99.68%, respectively, resulting in significantly lesser purge-gas emissions to the outside of the stack. The load-following test was successfully performed at a high ramp-up rate. The lifetime of the stack was confirmed by a 3500-h performance test, from which the degradation rate of the cell voltage was obtained. The advantages of the cascade-type stack were also confirmed by comparing its performance with that of a single-stage stack operating in dead-end mode.

  5. Ferroelectric polymer networks with high energy density and improved discharged efficiency for dielectric energy storage.

    PubMed

    Khanchaitit, Paisan; Han, Kuo; Gadinski, Matthew R; Li, Qi; Wang, Qing

    2013-01-01

    Ferroelectric polymers are being actively explored as dielectric materials for electrical energy storage applications. However, their high dielectric constants and outstanding energy densities are accompanied by large dielectric loss due to ferroelectric hysteresis and electrical conduction, resulting in poor charge-discharge efficiencies under high electric fields. To address this long-standing problem, here we report the ferroelectric polymer networks exhibiting significantly reduced dielectric loss, superior polarization and greatly improved breakdown strength and reliability, while maintaining their fast discharge capability at a rate of microseconds. These concurrent improvements lead to unprecedented charge-discharge efficiencies and large values of the discharged energy density and also enable the operation of the ferroelectric polymers at elevated temperatures, which clearly outperforms the melt-extruded ferroelectric polymer films that represents the state of the art in dielectric polymers. The simplicity and scalability of the described method further suggest their potential for high energy density capacitors. PMID:24276519

  6. Interaction of linear cationic peptides with phospholipid membranes and polymers of sialic acid.

    PubMed

    Kuznetsov, A S; Dubovskii, P V; Vorontsova, O V; Feofanov, A V; Efremov, R G

    2014-05-01

    Polysialic acid (PSA) is a natural anionic polymer typically occurring on the outer surface of cell membranes. PSA is involved in cell signaling and intermolecular interactions with proteins and peptides. The antimicrobial potential of peptides is usually evaluated in model membranes consisting of lipid bilayers but devoid of either PSA or its analogs. The goal of this work was to investigate the possible effect of PSA on the structure of melittin (Mlt) and latarcins Ltc1K, Ltc2a, and the activity of these peptides with respect to model membranes. These peptides are linear cationic ones derived from the venom of bee (Mlt) and spider (both latarcins). The length of each of the peptides is 26 amino acid residues, and they all have antimicrobial activity. However, they differ with respect to conformational mobility, hydrophobic characteristics, and overall charge. In this work, using circular dichroism spectroscopy, we show that the peptides adopt an α-helical conformation upon interaction with either PSA or phospholipid liposomes formed of either zwitterionic or anionic phospholipids or their mixtures. The extent of helicity depends on the amino acid sequence and properties of the medium. Based on small angle X-ray scattering data and the analysis of the fluorescence spectrum of the Trp residue in Mlt, we conclude that the peptide forms an oligomeric complex consisting of α-helical Mlt and several PSA molecules. Both latarcins, unlike Mlt, the most hydrophobic of the peptides, interact weakly with zwitterionic liposomes. However, they bind anionic liposomes or those composed of anionic/zwitterionic lipid mixtures. Latarcin Ltc1K forms associates on liposomes composed of zwitterionic/anionic lipid mixture. The structure of the peptide associates is either disordered or of β-sheet conformation. In all other cases the studied peptides adopt predominately α-helical conformation. In addition, we demonstrate that PSA inhibits membranolytic activity of Mlt and latarcin

  7. Degradation and reliability modelling of polymer electrolyte membrane (PEM) fuel cells

    NASA Astrophysics Data System (ADS)

    Fowler, Michael William

    To date there has been very little reliability or end of life analysis conducted for polymer electrolyte membrane (PEM) fuel cell systems. Voltage degradation as a fuel cell ages is a widely observed phenomenon, but little systematic information has been reported, nor has this phenomenon been included in electrochemical models. This work documents and classifies the failure modes that can be experienced in PEM fuel cells. A test station was adapted for the long term operation of a single, 50 cm2, internally hydrated, PEM fuel cell. An endurance test was conducted to age the cell under normal operating conditions for 1350 hours, at which time membrane failure was experienced. Changes in the polarization curve predicted by the Generalized Steady State Electrochemical Degradation Model (GSSEDM) are demonstrated from the data for the performance of typical PEM fuel cell hardware. This work develops and applies the generalized steady state electrochemical model for a PEM cell, and introduces two new terms to account for membrane electrode assembly (MEA) ageing, specifically the ageing of the MEA materials. One term is based on the concept that the water carrying capacity of the membrane deteriorates with time-in-service. The second term involves intrinsic rate constants associated with the reactions on the anode and cathode side, and the changes in catalytic activity due to catalyst degradation. The resulting model is largely mechanistic with most terms being derived from theory or including coefficients that have a theoretical basis, but also includes empirical parameters to deal with the changing performance. The value of such a generic model to predict or correlate PEM fuel cell stack voltages over the life of the fuel cell is demonstrated in this work. From the experimental data a membrane conductivity degradation rate, lambdaDR, was determined, and the value for lambdaDR was found to be -0.0007 hr -1. A term was introduced for degradation rate of the fuel cell due

  8. Analysis of Entanglement Length and Segmental Order Parameter in Polymer Networks

    NASA Astrophysics Data System (ADS)

    Lang, M.; Sommer, J.-U.

    2010-04-01

    The tube model of entangled chains is applied to compute segment fluctuations and segmental orientational order in polymer networks. The entanglement length Ne is extracted directly from monomer fluctuations without constructing a primitive path. Sliding motion of monomers along the tube axis leads to reduction of segmental order along the chain. For network strands of length N≫Ne, the average segmental order decreases ˜(NeN)-1/2 in marked contrast to the 1/Ne contribution of entanglements to network elasticity. As a consequence, network modulus is not proportional to segmental order in entangled polymer networks. Monte Carlo simulations over a wide range of molecular weights are in quantitative agreement with our theoretical predictions. The impact of entanglements on these properties is directly tested by comparing with simulations where entanglement constraints are switched off.

  9. Development and evaluation of electromembrane extraction across a hollow polymer inclusion membrane.

    PubMed

    Mamat, Nor Akma; See, Hong Heng

    2015-08-01

    In this work, a new variation of the electromembrane extraction (EME) approach employing a hollow polymer inclusion membrane (HPIM) was developed. In this method, a HPIM was prepared by casting a solution of the desired proportions of cellulose acetate (CTA), tris(2-ethylhexyl)phosphate (TEHP) and di-(2-ethylhexyl)phosphoric acid (D2EHPA) in dichloromethane on glass capillary tubing. Three basic drugs namely amphetamine, methamphetamine, and 3,4-methylenedioxy-N-methylamphetamine (MDMA) were selected as model analytes to evaluate the extraction performance of this new approach. The drugs were extracted from human plasma samples, through a 20μm thickness HPIM, to an aqueous acceptor solution inside the lumen of the hollow membrane. Parameters affecting the extraction efficiency were investigated in detail. Under the optimized conditions, enrichment factors in the range of 97-103-fold were obtained from 3mL of sample solution with a 10min extraction time and an applied voltage of 300V across the HPIM. The detection limits of the method for the three drugs were in the range of 1.0-2.5ng/mL (at a signal/noise ratio of three), with relative standard deviations of between 6.4% and 7.9%. When the method was applied to spiked plasma samples, the relative recoveries ranged from 99.2% to 100.8%. Enrichment factors of 103, 99 and 97 were obtained for amphetamine, methamphetamine, and MDMA, respectively. A comparison was also made between the newly developed approach and EME using supported liquid membranes (SLM) as well as standard sample preparation methods (liquid-liquid extraction) used by the Toxicology Unit, Department of Chemistry, Malaysia. PMID:26141273

  10. Surface morphology changes of polymer membrane and carbon paste sertraline sensors.

    PubMed

    Khater, M M; Hassib, H B; Issa, Y M; Mohammed, S H

    2015-03-01

    Polymer membrane and chemically modified carbon paste (CMCP) sensors for determination of sertraline HCl (Ser-Cl) incorporating sertraline tetraphenylborate (Ser-TPB) as an electro-active material were constructed. They showed a rapid and linear response for Ser-ion over the concentration range 0.01-10.00 mmol L(-1). The limits of detection were 2.80 and 9.55 μmol L(-1), and Nernastian slopes were 56.60, 59.60 mV decade(-1) for membrane and CMCP sensors for batch method. In flow injection analysis (FIA), the electrodes revealed comparatively good selectivity for Ser-ion with regard to a wide variety of different cations, sugars, and amino acids. The addition of different anionic additives, namely sodium tetraphenylborate (NaTPB), potassium tetraphenylborate (KTPB), potassium tetrakis[3,5-bis-(triflouromethyl)phenyl]borate (KTFMPB), and sodium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate (NaTFMPB), to the prepared mixture improved their response characteristics. The surface morphologies of membrane films containing PVC only (blank), plasticizer+PVC, Ser-TPB+plasticizer+PVC, and Ser-TPB +plasticizer+PVC+additive were studied using scanning and atomic force electron microscopes. These sensors had been used in the potentiometric titration of Ser-ion against NaTPB. Standard addition method for the pure raw material and some of its pharmaceutical tablets was used for Ser-Cl determination. The obtained results were tested for their repeatability and reproducibility and were statistically treated by F- and t- tests. PMID:25618706

  11. Network of nano-droplets by a tri-block polymer

    NASA Astrophysics Data System (ADS)

    Sharifi, Soheil; Doodman, Esmaeil

    2014-11-01

    Mixtures of oil in water nano-droplets with two molecular weights of a tri-block polymer was studied by quasi elastic light scattering and small angle X-ray scattering. The results showed that the size and interaction of droplets didn't change with increase of the tri-block polymer length but the order parameters increased. The increase of length of the tri-block biopolymer changed the dynamics of the droplets. A network formation is resulted with increase of the amount of tri-block polymer in the microemulsions.

  12. U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications

    PubMed Central

    Houchins, Cassidy; Kleen, Greg J.; Spendelow, Jacob S.; Kopasz, John; Peterson, David; Garland, Nancy L.; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C.

    2012-01-01

    Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed. PMID:24958432

  13. U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications.

    PubMed

    Houchins, Cassidy; Kleen, Greg J; Spendelow, Jacob S; Kopasz, John; Peterson, David; Garland, Nancy L; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C

    2012-01-01

    Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed. PMID:24958432

  14. Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive.

    PubMed

    Zhao, Yi-Fan; Zhang, Pei-Bin; Sun, Jian; Liu, Cui-Jing; Yi, Zhuan; Zhu, Li-Ping; Xu, You-Yi

    2015-06-15

    Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc. PMID:25752579

  15. Structural basis of dynamic membrane recognition by trans-Golgi network specific FAPP proteins.

    PubMed

    Lenoir, Marc; Grzybek, Michał; Majkowski, Michał; Rajesh, Sandya; Kaur, Jaswant; Whittaker, Sara B-M; Coskun, Ünal; Overduin, Michael

    2015-02-27

    Glycosphingolipid metabolism relies on selective recruitment of the pleckstrin homology (PH) domains of FAPP proteins to the trans-Golgi network. The mechanism involved is unclear but requires recognition of phosphatidylinositol-4-phosphate (PI4P) within the Golgi membrane. We investigated the molecular basis of FAPP1-PH domain interactions with PI4P bilayers in liposome sedimentation and membrane partitioning assays. Our data reveals a mechanism in which FAPP-PH proteins preferentially target PI4P-containing liquid disordered membranes, while liquid ordered membranes were disfavored. Additionally, NMR spectroscopy was used to identify the binding determinants responsible for recognizing trans-Golgi network-like bicelles including phosphoinositide and neighboring lipid molecules. Membrane penetration by the FAPP1-PH domain was mediated by an exposed, conserved hydrophobic wedge next to the PI4P recognition site and ringed by a network of complementary polar residues and basic charges. Our data illuminates how insertion of a structured loop provides selectivity for sensing membrane fluidity and targeting to defined membrane zones and organelles. The determinants of this membrane sensing process are conserved across the CERT, OSBP and FAPP family. Hence, lipid gradients not only result in differential membrane ordering along the secretory pathway but also specifically localize diverse proteins through recognition of ensembles of lipid ligands in dynamic and deformable bilayers in order to promote anterograde trafficking. PMID:25579996

  16. Constructing proton-conductive highways within an ionomer membrane by embedding sulfonated polymer brush modified graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhao, Liping; Li, Yifan; Zhang, Haoqin; Wu, Wenjia; Liu, Jindun; Wang, Jingtao

    2015-07-01

    Sulfonated polymer brush modified graphene oxide (SP-GO) fillers with controllable brush length are synthesized via the facile distillation-precipitation polymerization, and then incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to fabricate composite membranes. The influences of SP-GO upon the microstructures, including thermal and mechanical properties, water uptake/swelling, proton conduction, H2 permeability and single PEMFC performances of composite membranes are intensively investigated. It is found that the SP-GO fillers are uniformly dispersed and tend to lie perpendicularly to the cross-section surface of the whole membrane, which allow SP-GO fillers creating inter-connected and broad ionic pathways through the sulfonic acid groups in polymer brushes. Meanwhile, the SP-GO fillers connect the ionic clusters in SPEEK matrix via interfacial interactions. In such a way, proton-transfer highways are constructed along the SPEEK/SP-GO interface, which lower the proton transfer activation energy and enhance the proton conductivities of the composite membranes under both hydrated and anhydrous conditions. Furthermore, elevating the brush length on SP-GO could further enhance the proton conductivity. Compared to SPEEK control membrane, a 95.5% increase in hydrated conductivity, an 178% increase in anhydrous conductivity and a 37% increase in maximum power density are obtained for the optimal composite membrane.

  17. New approaches towards novel composite and multilayer membranes for intermediate temperature-polymer electrolyte fuel cells and direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Branco, Carolina Musse; Sharma, Surbhi; de Camargo Forte, Maria Madalena; Steinberger-Wilckens, Robert

    2016-06-01

    This review analyses the current and existing literature on novel composite and multilayer membranes for Polymer Electrolyte Fuel Cell applications, including intermediate temperature polymer electrolyte fuel cell (IT-PEFC) and direct methanol fuel cell (DMFC) systems. It provides a concise scrutiny of the vast body of literature available on organic and inorganic filler based polymer membranes and links it to the new emerging trend towards novel combinations of multilayered polymer membranes for applications in DMFC and IT-PEFC. The paper carefully explores the advantages and disadvantages of the most common preparation techniques reported for multilayered membranes such as hot-pressing, casting and dip-coating and also summarises various other fresh and unique techniques employed for multilayer membrane preparation.

  18. Modeling of hydro-thermo-mechanical behavior of Nafion NRE212 for Polymer Electrolyte Membrane Fuel Cells using the Finite Viscoplasticity Theory Based on Overstress for Polymers (FVBOP)

    NASA Astrophysics Data System (ADS)

    Colak, Ozgen U.; Acar, Alperen

    2013-08-01

    The primary aim of this work is to present the modifications made to the Finite Viscoplasticity Theory Based on Overstress for Polymers (FVBOP). This is a unified state variable theory and the proposed changes are designed to account for humidity and temperature effects relevant to the modeling of the hydrothermal deformation behavior of ionomer membranes used in Polymer Electrolyte Membrane Fuel Cells (PEMFC). Towards that end, the flow function, which is responsible for conferring rate dependency in FVBOP, is modified. A secondary objective of this work was to investigate the feasibility of using the storage modulus obtained by Dynamic Mechanical Analysis (DMA) in place of the elasticity modulus obtained from conventional tensile/compressive tests, and find the correlation between the storage modulus and the elasticity modulus. The numerical simulations were juxtaposed against data from tensile monotonic loading and unloading experiments on perfluorosulfonic acid (PFSA) membrane Nafion NRE212 samples which are used extensively as a membrane material in PEMFC. The deformation behavior was modeled at four different temperatures (298, 323, 338, and 353 K—all values below the glass transition temperature of Nafion) and at three water content levels (3, 7 and 8 % swelling). The effects of strain rate, temperature, and hydration were captured well with the modified FVBOP model.