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Sample records for solid polymers crosslinking

  1. Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

    NASA Astrophysics Data System (ADS)

    Lu, Canhui; Zhang, Xinxing; Zhang, Wei

    2015-05-01

    The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

  2. Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

    SciTech Connect

    Lu, Canhui; Zhang, Xinxing; Zhang, Wei

    2015-05-22

    The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

  3. Interfacial fracture between highly crosslinked polymer networks and a solid surface: Effect of interfacial bond density

    SciTech Connect

    STEVENS,MARK J.

    2000-03-23

    For highly crosslinked, polymer networks bonded to a solid surface, the effect of interfacial bond density as well as system size on interfacial fracture is studied molecular dynamics simulations. The correspondence between the stress-strain curve and the sequence of molecular deformations is obtained. The failure strain for a fully bonded surface is equal to the strain necessary to make taut the average minimal path through the network from the bottom solid surface to the top surface. At bond coverages less than full, nanometer scale cavities form at the surface yielding an inhomogeneous strain profile. The failure strain and stress are linearly proportional to the number of bonds at the interface unless the number of bonds is so few that van der Waals interactions dominate. The failure is always interfacial due to fewer bonds at the interface than in the bulk.

  4. Cross-linking of Ordered Pluronic/Ionic Liquid Blends for Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Miranda, Daniel; Versek, Craig; Tuominen, Mark; Watkins, James; Russell, Thomas

    2012-02-01

    Ion gels were fabricated by cross-linking PPO-PEO-PPO triblock copolymers swollen in a room temperature ionic liquid (IL). The copolymers are modified by esterification to replace the terminal hydroxyl endgroups with methacrylate endgroups. This allows the copolymer/IL blends to be cross-linked by a UV cure, forming a gel. The strong interaction of the IL with the PEO block suppresses PEO crystallization which is necessary for good ion conduction. In addition, the interaction between the IL and PEO is strongly selective for PEO, strengthening microphase separation. Despite this, the low molecular weight copolymers remain disordered in the melt even when blended with the IL. However, high molecular weight copolymers are capable of microphase separating into highly ordered block copolymer morphologies. This difference allows the effect of microphase separation on ion transport to be studied. The effect of block copolymer composition is also studied, by varying the PEO fraction of the copolymer. The resultant gels show high ionic conductivity and solid-like behavior, indicating that these materials may be effective as solid polymer electrolytes.

  5. All Solid-State Lithium Metal Batteries Using Cross-linked Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Pan, Qiwei; Li, Christopher; Soft Materials Team

    Nowadays, to prepare all solid-state lithium metal batteries with high rate capability and stability using solid polymer electrolytes (SPEs) is still a grand challenge because of the interfaces between the SPE and the electrodes. In this presentation, we report a series of hybrid SPEs with controlled network structures by using POSS as cross-linker. These hybrid network SPEs show promising ionic conductivity, mechanical properties, and lithium dendrite growth resistance. All solid-state LiFePO4/Li batteries were also prepared using these SPEs as the electrolytes to study the effect of conductivity and mechanical properties of the SPEs on the performance of the batteries. At 90 °C, the prepared cells show high rate capability and stability. Capacity up to 160 mAh/g can be obtained at a C/2 rate during the galvanostatic cycling. Capacity retention of the cells is higher than 80% after 250 cycles. Battery performance at 60 °C and decay mechanism of the batteries will also be discussed.

  6. Gas-phase transfer of polymer cross-linking agents and by-products to solid oral pharmaceuticals.

    PubMed

    Maus, Russell G; Li, Min; Clement, Christopher M; Kinzer, Jeffery A

    2007-11-01

    In the pharmaceutical industry, solid oral compressed tablets (OCT) are frequently transported in bulk containers prior to packaging. While in this state, the product is generally protected from interaction with liquid and solid contaminants by physical barriers (e.g., polyethylene bags, drums, etc.). Vapor phase contamination, although generally less frequently observed, is possible. A specific example of the detection and identification of volatile by-products (acetophenone and 2-phenyl-2-propanol) of a common polymer cross-linking agent (dicumyl peroxide) is presented. The product tablets were compressed, placed into double polyethylene bags, and subsequently placed into a polyethylene drum for shipment overseas. To cushion the product during transit, a cross-linked polyethylene foam disk (designed to fit into the bottom of the drum) was placed below the bag of tablets. Initially, these contaminants were detected by HPLC with UV detection at the receiving laboratory, and assumed to be degradates of the active components of the product. Further analysis showed that neither the collected UV absorbance data nor the observed levels of the contaminants were consistent with known degradates of the product. Liquid extraction followed by GC-MS analysis of the product as well as the cross-linked foam disk exhibited measurable quantities of the contaminants in question. Vapor phase transfer of these cross-linking agent by-products, originating in the cross-linked foam pads, was determined to be the root cause for the presence of these compounds in the product. PMID:17686599

  7. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1997-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  8. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1998-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  9. Radiation induced estane polymer crosslinking

    SciTech Connect

    Fletcher, M.; Foster, P.

    1997-12-01

    The exposure of polymeric materials to radiation has been known to induce the effects of crosslinking and degradation. The crosslinking phenomena comes about when two long chain polymers become linked together by a primary bond that extends the chain and increases the viscosity, molecular weight and the elastic modules of the polymer. This process has been observed in relatively short periods of time with fairly high doses of radiation, on the order of several megarads/hour. This paper address low dose exposure over long periods of time to determine what the radiation effects are on the polymeric binder material in PBX 9501. An experimental sample of binder material without explosives will be placed into a thermal and radiation field produced from a W-48 put mod 0. Another sample will be placed in a thermal environment without the radiation. The following is the test plan that was submitted to the Pantex process. The data presented here will be from the first few weeks of exposure and this test will be continued over the next few years. Subsequent data will hopefully be presented in the next compatibility and aging conference.

  10. Microbes encapsulated within crosslinkable polymers

    SciTech Connect

    Chidambaram, Devicharan; Liu, Ying; Rafailovich, Miriam H

    2013-02-05

    The invention relates to porous films comprising crosslinked electrospun hydrogel fibers. Viable microbes are encapsulated within the crosslinked electrospun hydrogel fibers. The crosslinked electrospun hydrogel fibers are water insoluble and permeable. The invention also relates to methods of making and using such porous films.

  11. Viscoelastic behavior of polymers undergoing crosslinking reactions.

    NASA Technical Reports Server (NTRS)

    Moacanin, J.; Aklonis, J. J.

    1971-01-01

    Previously a method was developed for predicting the viscoelastic response of polymers undergoing scission reactions. These results are now extended to include crosslinking reactions. As for scission, at any given time the character of the network chains is determined by the instantaneous crosslink density. For scission all chains were assumed to carry the same stress; for crosslinking, however, the stress is distributed between the 'new' and 'old' chains. Equations for calculating the creep response of a system which experiences a step increase in crosslink density are derived.

  12. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, W.P. Jr.; Apen, P.G.; Mitchell, M.A.

    1998-01-20

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes. 1 fig.

  13. A Single Molecular Diels-Alder Crosslinker for Achieving Recyclable Cross-Linked Polymers.

    PubMed

    Chen, Shengli; Wang, Fenfen; Peng, Yongjin; Chen, Tiehong; Wu, Qiang; Sun, Pingchuan

    2015-09-01

    A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers. PMID:26248230

  14. Driven Polymer Translocation into a Crosslinked Gel

    NASA Astrophysics Data System (ADS)

    Sean, David; Slater, Gary

    2015-03-01

    In a typical polymer translocation setup, a thin membrane is used to separate two chambers and a polyelectrolyte is driven by an electric field to translocate from one side of the membrane to the other via a small nanopore. However, the high translocation rate that results from the forces required to drive this process makes optical and/or electrical analysis of the translocating polymer challenging. Using coarse-grained Langevin Dynamics simulations we investigate how the translocation process can be slowed down by placing a crosslinked gel on the trans-side of the membrane. Since the driving electric field is localized in the neighborhood of the nanopore, electrophoretic migration is only achieved by a ``pushing'' action from the polymer segment residing in the nanopore. For the case of a flexible polymer we find that the polymer fills the gel pores via multiple ``herniation'' processes, whereas for a semi-flexible chain in a tight gel there are no hernias and the polymer follows a smooth curvilinear path. Moreover, for the case of a semi-flexible polymer the gel makes the translocation process more uniform by reducing the acceleration at the end of the process.

  15. Highly crosslinked silicon polymers for gas chromatography columns

    NASA Technical Reports Server (NTRS)

    Shen, Thomas C. (Inventor)

    1994-01-01

    A new highly crosslinked silicone polymer particle for gas chromatography application and a process for synthesizing such copolymer are described. The new copolymer comprises vinyltriethoxysilane and octadecyltrichlorosilane. The copolymer has a high degree of crosslinking and a cool balance of polar to nonpolar sites in the porous silicon polymer assuring fast separation of compounds of variable polarity.

  16. Crosslinked crystalline polymer and methods for cooling and heating

    DOEpatents

    Salyer, Ival O.; Botham, Ruth A.; Ball, III, George L.

    1980-01-01

    The invention relates to crystalline polyethylene pieces having optimum crosslinking for use in storage and recovery of heat, and it further relates to methods for storage and recovery of heat using crystalline polymer pieces having optimum crosslinking for these uses. Crystalline polymer pieces are described which retain at least 70% of the heat of fusion of the uncrosslinked crystalline polymer and yet are sufficiently crosslinked for the pieces not to stick together upon being cycled above and below the melting point of said polymer, preferably at least 80% of the heat of fusion with no substantial sticking together.

  17. Recovery system containing lanthanide-crosslinked polymers

    SciTech Connect

    Dovan, H.T.; Hutchins, R.D.

    1993-07-13

    A recovery system is described comprising: (a) a subterranean formation; (b) a well bore penetrating at least a portion of the subterranean formation; and (c) a composition capable of forming a gel present in at least a portion of the well bore, wherein the composition comprises: (i) a crosslinkable polymer (CP) selected from the group consisting of heteropolysaccharides obtained by the fermentation of starch-derived sugar, ammonium salts, and alkali metal salts; (ii) a lanthanide; and (iii) an ingredient selected from the group consisting of gel breakers, sequestering agents, proppants for use in hydraulically fracturing, particulate agents for forming a gravel pack, and base precursors selected from the group consisting of ammonium slats, urea, thiourea, and mixtures of these. A second recovery system is described in which the gel composition comprises: (i) a CP selected from the group consisting of acrylic acid-acrylamide copolymers, acrylic acid-methacrylamide copolymers, polyacrylamides, polymethacrylamides, partially hydrolyzed polyacrylamides, partially hydrolyzed polymethacrylamides, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyalkyleneoxides, lignosulfonates, ammonium salts, alkali metal salts, and alkaline earth salts of lignosulfonates; and (ii) a crosslinking agent selected from the group consisting of lanthanides, sequestered lanthanides, and mixtures thereof. A third system is described in which the gel composition comprises: (i) a CP, hydroxyethylcellulose; and (ii) a crosslinking agent selected from the group consisting of lanthanides, sequestered lanthanides, and mixtures thereof. A fourth system is described in which the gel composition comprises: (i) a CP selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyalkyleneoxides, lignosulfonates, ammonium salts, alkali metal salts, and alkaline earth salts of lignosulfonates; and (ii) a lanthanide.

  18. 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.

  19. Solid polymer electrolytes

    DOEpatents

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

    1995-01-01

    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

  20. Solid polymer electrolytes

    DOEpatents

    Abraham, K.M.; Alamgir, M.; Choe, H.S.

    1995-12-12

    This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

  1. Photomobile polymer materials: photoresponsive behavior of cross-linked liquid-crystalline polymers with mesomorphic diarylethenes.

    PubMed

    Mamiya, Jun-ichi; Kuriyama, Akito; Yokota, Naoki; Yamada, Munenori; Ikeda, Tomiki

    2015-02-16

    Cross-linked liquid-crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross-linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross-linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed-ring to open-ring isomerization, the bent films revert to the initial flat state. Without visible-light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross-linked diarylethene LC polymers. PMID:25581255

  2. Solid polymer electrolyte compositions

    DOEpatents

    Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

    2001-01-01

    An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

  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. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers.

    PubMed

    Hearon, K; Gall, K; Ware, T; Maitland, D J; Bearinger, J P; Wilson, T S

    2011-07-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at T(g), and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials. PMID:21572577

  5. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers

    PubMed Central

    Hearon, K.; Gall, K.; Ware, T.; Maitland, D. J.; Bearinger, J. P.; Wilson, T. S.

    2011-01-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at Tg, and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials. PMID:21572577

  6. Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas

    2006-01-01

    Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X

  7. 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.

  8. Photonic multilayer sensors from photo-crosslinkable polymer films

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan C.

    2012-02-01

    Photo-crosslinkable copolymers containing pendent benzophenone (BP) groups provide a convenient means to fabricate multilayer polymer films. We describe the preparation of alternating multilayers of photo-crosslinkable poly(N-isopropylacrylamide) (PNIPAM), a water-swellable, temperature sensitive polymer, and poly(para-methylstyrene) (PpMS), a non-swellable polymer, by sequential spin-coating and photo-crosslinking. This route provides well-defined layered structures with minimal interfacial broadening between layers and uniformity of thickness from layer to layer as determined by dynamic secondary ion mass spectrometry (d-SIMS). Appropriate choices of layer thicknesses yield 1-D photonic gel sensors. The reflectance peak is shifted through the visible spectrum upon swelling or de-swelling of the PNIPAM layers in water, providing an accessible means for colorimetric temperature sensing.

  9. 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.

  10. 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.

  11. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  12. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, M.; Abraham, K.M.

    1993-10-12

    This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

  13. Rechargeable solid polymer electrolyte battery cell

    DOEpatents

    Skotheim, Terji

    1985-01-01

    A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

  14. Process for crosslinking and extending conjugated diene-containing polymers

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

    1977-01-01

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

  15. 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

  16. Mechanical properties of crosslinked polymer coatings

    NASA Technical Reports Server (NTRS)

    Csernica, Jeffrey

    1994-01-01

    The objectives of this experiment are to: fabricate and test thin films to explore relations between a polymer's structure and its mechanical properties; expose students to testing methods for hardness and impact energy that are simple to perform and which have results that are easy to comprehend; show importance of polymer properties in materials that students frequently encounter; illustrate a system which displays a tradeoff between strength and impact resistance, the combination of which would need to be optimized for a particular application; and to expose students to coatings technology and testing.

  17. Photocontrolled Cargo Release from Dual Cross-Linked Polymer Particles.

    PubMed

    Tan, Shereen; Cui, Jiwei; Fu, Qiang; Nam, Eunhyung; Ladewig, Katharina; Ren, Jing M; Wong, Edgar H H; Caruso, Frank; Blencowe, Anton; Qiao, Greg G

    2016-03-01

    Burst release of a payload from polymeric particles upon photoirradiation was engineered by altering the cross-linking density. This was achieved via a dual cross-linking concept whereby noncovalent cross-linking was provided by cyclodextrin host-guest interactions, and irreversible covalent cross-linking was mediated by continuous assembly of polymers (CAP). The dual cross-linked particles (DCPs) were efficiently infiltrated (∼80-93%) by the biomacromolecule dextran (molecular weight up to 500 kDa) to provide high loadings (70-75%). Upon short exposure (5 s) to UV light, the noncovalent cross-links were disrupted resulting in increased permeability and burst release of the cargo (50 mol % within 1 s) as visualized by time-lapse fluorescence microscopy. As sunlight contains UV light at low intensities, the particles can potentially be incorporated into systems used in agriculture, environmental control, and food packaging, whereby sunlight could control the release of nutrients and antimicrobial agents. PMID:26862769

  18. Preparation of crosslinked 1,2,4-oxadiazole polymer

    NASA Technical Reports Server (NTRS)

    Rosser, R. W.; Shalhoub, I. M.; Kwong, H. (Inventor)

    1981-01-01

    New crosslinked 1,2,4-oxadiazole elastomers were prepared by thermally condensing a monomer having the formula H2N(HON)C-R-Q, wherein Q is a triazine ring-forming group such as nitrile or amidine or a mixture of such group with amidoxime, or a mixture of said monomer with R C(NOH)NH2 sub 2 with R in these formulas standing for a bivalent organic radical. In the monomer charge, the overall proportions of amidoxime groups to triazine ring-forming groups varies depending on the extent of crosslinking desired in the final polymer.

  19. Photo-crosslinkable polymers for fabrication of photonic multilayer sensors

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan C.

    2013-03-01

    We have used photo-crosslinkable polymers to fabricate photonic multilayer sensors. Benzophenone is utilized as a covalently incorporated pendent photo-crosslinker, providing a convenient means of fabricating multilayer films by sequential spin-coating and crosslinking processes. Colorimetric temperature sensors were designed from thermally-responsive, low-refractive index poly(N-isopropylacrylamide) (PNIPAM) and high-refractive index poly(para-methyl styrene) (P pMS). Copolymer chemistries and layer thicknesses were selected to provide robust multilayer sensors which show color changes across nearly the full visible spectrum due to changes in temperature of the hydrated film stack. We have characterized the uniformity and interfacial broadening within the multilayers, the kinetics of swelling and de-swelling, and the reversibility over multiple hydration/dehydration cycles. We also describe how the approach can be extended to alternative sensor designs through the ability to tailor each layer independently, as well as to additional stimuli by selecting alternative copolymer chemistries.

  20. Tunable photonic multilayer sensors from photo-crosslinkable polymers

    NASA Astrophysics Data System (ADS)

    Chiappelli, Maria; Hayward, Ryan

    2014-03-01

    The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

  1. Simulations of Polymer Crazing: Effect of Crosslinks and Dilution

    NASA Astrophysics Data System (ADS)

    Robbins, Mark O.; Barsky, Sandra

    2000-03-01

    Molecular dynamics simulations were used to study the growth and structure of crazes in adhesive films of entangled linear polymers that have been either (a) crosslinked or (b) diluted by smaller molecules. The films were ruptured by separating the two bounding walls (adherends) at a small constant velocity. In all systems the force on the walls rose to the same value before the first yield event caused cavities to form in the film. These cavities grew as the walls were displaced further. In systems that formed a stable craze, cavity growth was eventually stopped by entanglements or crosslinks. Stress concentrations then caused new cavities to form in neighboring regions. This process continued at a constant plateau stress until the entire film had been stretched by an extension ratio λ. The plateau stress increased slightly with increasing crosslink density, and decreased with decreasing fraction of long chains in diluted systems. As in experiments, when the fraction decreased below about 30plateau stress vanished and there was no longer a stable craze. The extension ratio fell with increasing crosslink density and rose as the fraction of long chains dropped. These changes can be fit with a simple geometric model based on the ability to stretch a random coil whose length is the mean spacing between crosslinks or entanglements. No chain scission was found for reasonable bond strengths. Void formation and elastic constants were also studied.

  2. Polymer-additive extraction via pressurized fluids and organic solvents of variously cross-linked poly(methylmethacrylates).

    PubMed

    Nazem, N; Taylor, L T

    2002-04-01

    Variously cross-linked poly(methylmethacrylates) (PMMAs) are synthesized with three additives incorporated at theoretically 1000 microg of the additive per gram of prepared polymer. The additives are Irganox 1010, Irganox 1076, and Irgafos 168. The in-house" synthesized polyacrylates are then subjected to supercritical fluid extraction (SFE) to determine if additive recovery is a function of percent cross-linking. Although considerable work in this regard has been performed with non-cross-linked polyolefins, the literature is lacking regarding polyacrylates. Some additive degradation apparently occurs during the synthesis, as judged by the increased complexity of the extract high-performance liquid chromatographic trace and the low percent recoveries observed especially for the Irganoxes. For low polymer cross-linking (1%), it appears that both PMMA synthetic reproducibility and readily observed polymer swelling during SFE are serious issues that adversely affect additive percent recovery and precision of results. Higher percent cross-linking yields more consistent analytical data than low percent cross-linking, even though the amount of additive extracted in all PMMA samples (regardless of cross-linking percentage) is essentially the same whether the extraction is via SFE or liquid-solid extraction with methylene chloride. Results for comparably cross-linked poly(ethylmethacrylate) and poly(butylmethacrylate) are similar to PMMA. PMID:12004935

  3. Nonaffine chain and primitive path deformation in crosslinked polymers

    NASA Astrophysics Data System (ADS)

    Davidson, J. D.; Goulbourne, N. C.

    2016-08-01

    Chains in a polymer network deform nonaffinely at small length scales due to the ability for extensive microscopic rearrangement. Classically, the conformations of an individual chain can be described solely by an end-to-end length. This picture neglects interchain interactions and therefore does not represent the behavior of a real polymer network. The primitive path concept provides the additional detail to represent interchain entanglements, and techniques have recently been developed to identify the network of primitive paths in a polymer simulation. We use coarse-grained molecular dynamics (MD) to track both chain end-to-end and primitive path deformation in crosslinked polymer networks. The range of simulated materials includes short chain unentangled networks to long, entangled chain networks. Both chain end-to-end and primitive path length are found to be linear functions of the applied deformation, and a simple relationship describes the behavior of a network in response to large stretch uniaxial, pure shear, and equi-biaxial deformations. As expected, end-to-end chain length deformation is nonaffine for short chain networks, and becomes closer to affine for networks of long, entangled chains. However, primitive path deformation is found to always be nonaffine, even for long, entangled chains. We demonstrate how the microscopic constraints of crosslinks and entanglements affect nonaffine chain deformation as well as the simulated elastic behavior of the different networks.

  4. Kinetics of Microphase Separation in Crosslinked Polymer Blend

    SciTech Connect

    Bettachy, A.; Benhamou, M.; Derouiche, A.; Fazni, A.

    2009-04-19

    The solvent effect on the early kinetics of the microphase separation (MPS) in binary crosslinked polymer was studied. In the presence of a good solvent, calculations were done using first the random phase approximation method and second an extended blob model, where a crosslinked chain is viewed as a sequence having blobs as new units. Kinetics were studied through the variation of the relaxation rate, {tau}{sub q}, upon the wave number, q, in the region around the spinodal temperature. When the temperature is changed from an initial value, T{sub i}, toward the final value, T{sub f}, very close to the critical point, the only motion allowed to the crosslinked chains is of Rouse type because of the presence of the crosslinks. The swelling effect on the MPS leads to a multiplicative renormalization of critical parameters of the molten state by factors as power of the overall monomer volume fraction, {phi}. The characteristic frequency, {omega}{sub (q)}, inverse of {tau}{sub q}, scales as {omega}(q) congruent with q{sup 6}{epsilon}{sup 3}, where {epsilon} stands for the traditional screening length. The study of kinetics of MPS is then extended in the presence of a theta solvent.

  5. 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

  6. Chemistry of crosslinking processes for self-healing polymers.

    PubMed

    Billiet, Stijn; Hillewaere, Xander K D; Teixeira, Roberto F A; Du Prez, Filip E

    2013-02-25

    Recent developments in material design have seen an exponential increase of polymers and polymer composites that can repair themselves in response to damage. In this review, a distinction is made between extrinsic materials, where the self-healing property is obtained by adding healing agents to the material to be repaired, and intrinsic materials, where self-healing is achieved by the material itself through its chemical nature. An overview of the crosslinking chemistries used in self-healing materials will be given, discussing the advantages and drawbacks of each system. The review is not only aiming to enable researchers to compare their ongoing research with the state-of-the-art but also to serve as a guide for the newcomers, which allows for a selection of the most promising self-healing chemistries. PMID:23255325

  7. 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.

  8. A tour-de-force in polymer crosslinked aerogels

    NASA Astrophysics Data System (ADS)

    Mulik, Sudhir M.

    In the quest of building mechanically strong materials with low density and high porosity, polymer crosslinked aerogels stand as the most promising nano-engineered examples. Covalent attachment of polymers and bridging of skeletal nanoparticles of typical aerogels is demonstrated by using surface initiated polymerization (SIP) with a bidentate free-radical initiator structurally related to azobisisobutyronitrile (AIBN) and confined on mesoporous silica surfaces. Different monomers were introduced in the mesopores and upon heating at 70 °C, all mesoporous surfaces throughout the entire skeletal framework were coated conformally with a 10-12 nm thick polymer layer indistinguishable spectroscopically from the respective commercial bulk materials. The new materials combine hydrophobicity with vastly improved mechanical properties. Resorcinol formaldehyde (RF) aerogels are pursued as precursors of carbon aerogels, which are electrically conducting. We have developed a HCl-catalyzed gelation process in CH3CN, which is completed in ˜ 2 h at room temperature as opposed to the week-long base-catalyzed literature process. The final aerogels are spectroscopically indistinguishable from typical base-catalyzed samples. Carbon (C-) aerogels are made by pyrolysis of RF aerogels, and combine electrical conductivity with a high open mesoporosity. Nevertheless, macropores facilitate mass-transfer and they could be beneficial for applications in separations or as fuel cell and battery electrodes. Here, we report a method where an open macroporosity is introduced by pyrolysing RF aerogels whose skeletal nanoparticles have been coated conformally and crosslinked chemically with an isocyanate-derived polymer. The new macroporous material was evaluated electrochemically for possible application as an electrode in batteries and fuel cells.

  9. Optimizing end-group cross-linking polymer electrolytes for fuel cell applications

    SciTech Connect

    Kim, Yu Seung; Lee, Kwan Soo; Jeong, Myung - Hwan; Lee, Jae - Suk

    2009-01-01

    This paper demonstrates the optimization of proton conductivity and water uptake for cross-linkable polymer electrolytes through synthesis and characterization of end-group cross-linkable sulfonated poly(arylene ether) copolymers (ESF-BPs). The extent of reaction of cross-linking was controlled by reaction time resulting in a series of polymers with two, independent tunable parameters, degree of sulfonation (DS) and degree of cross-linking (DC). For the polymers presented, cross-linking improved proton conductivity while reducing water uptake, an uncommon trend in polymer electrolytes where water is critical for proton conduction. Other trends relating to changes are reported and the results yield insight into the role of DS and DC and how to optimize electrochemical properties and performance of polymer electrolytes through these tunable parameters. Select polymer electrolytes were tested in fuel cells where performance and durability with accelerated relative humidity cycling were compared with Nafion{reg_sign}.

  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. Microscopic mechanisms of the shape memory effect in crosslinked polymers

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    In this work we perform coarse-grained molecular dynamics (MD) simulations to study the molecular origins of the thermal shape memory effect in crosslinked polymer materials. Thermal shape memory polymers (SMPs) are materials able to hold a deformed shape when cooled below the glass transition temperature, and subsequently recover the initial shape when heated. To use SMPs in various applications requires materials which reliably hold and recover their shapes; this has sparked recent synthesis work to create new SMP materials with optimized properties. Here we use coarse-grained MD simulations with different polymer chain models to determine which parameters affect relevant SMP behavior and to investigate the molecular mechanisms at the level of individual chains during temperature cycling. The simulations show how temperature-dependent chain mobility leads to shape memory polymer behavior. In particular, we demonstrate the importance of attractive monomer interactions in leading to ‘good’ SMP behavior. The results suggest promising routes for material development. Additionally, the mechanisms identified with the simple simulation model can be used to inform multi-scale models of SMP material behavior.

  12. Solid polymer electrolyte photovoltaic cell

    SciTech Connect

    Skotheim, T.; Lundstrom, I.

    1982-04-01

    Solid photoelectrochemical cells are described based on PEO-KI/I/sub 2/ electrolytes, n-Si/Pt/PPy photoanodes, and conductive tin-oxide glass counter electrodes. The performance of the present devices is limited by a high series resistance in the polymer film. 22 refs.

  13. Structural, Vibrational, Thermal And Electrical Characterization Of Gamma Radiation-Crosslinked Poly (Vinyl Alcohol)-Based Solid Polymer Electrolytes Blended With LiOH{center_dot}H{sub 2}O Salt

    SciTech Connect

    Khafagy, Rasha M.; Madani, M.; Badr, Y. A.

    2008-09-23

    Solid polymer electrolytes based on poly(vinyl alcohol)(PVA) blended with different concentrations of LiOH{center_dot}H{sub 2}O salt were prepared using casting and {gamma}-irradiation techniques. The structure and blending of the poly-electrolytes were studied by X-ray diffraction (XRD) and Fourier transform Raman spectroscopy. The thermal properties of these solid polymer electrolytes were examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The XRD spectra for the electrolytes indicated that the crystalline ratio of PVA decreases with the concentration of Lithium salt. Crystallinity, isotacticity and syndiotacticity percentages were also determined from Raman spectra at different salt concentrations revealing that the crystallinity and the Isotactic regularity of PVA molecule is reduced with salt addition, while the syndiotacticity increases linearly. DSC thermograms showed good accordance with these facts by detecting two melting temperatures corresponding to the two regularities, and these melting points change with the salt content. All characterizing techniques revealed the blend formation between LiOH{center_dot}H{sub 2}O salt and the polymer matrix. To account for the performance of the prepared solid polymer electrolytes, thermally stimulated depolarization current (TSDC) studies of the prepared blends were done. Short circuit TSDC at a polarizing temperature 353 K with a polarizing field of 3 kV cm{sup -1} have been analyzed in the temperature range 300-410 K. Two peaks are evident from the global TSDC measurements on the pure PVA homopolymer. Meanwhile, in all blended samples; there is only one broad peak with a shoulder on the high temperature side due to the relaxation of the poly-blend system. The prepared solid polymer electrolytes showed good charge storage capacity, and moderate current density values near the ambient.

  14. Differentially photo-crosslinked polymers enable self-assembling microfluidics

    PubMed Central

    Jamal, Mustapha; Zarafshar, Aasiyeh M.; Gracias, David H.

    2012-01-01

    An important feature of naturally self-assembled systems such as leaves and tissues is that they are curved and have embedded fluidic channels that enable the transport of nutrients to, or removal of waste from, specific three-dimensional (3D) regions. Here, we report the self-assembly of photopatterned polymers, and consequently microfluidic devices, into curved geometries. We discovered that differentially photo-crosslinked SU-8 films spontaneously and reversibly curved upon film de-solvation and re-solvation. Photolithographic patterning of the SU-8 films enabled the self-assembly of cylinders, cubes, and bidirectionally folded sheets. We integrated polydimethylsiloxane (PDMS) microfluidic channels with these SU-8 films to self-assemble curved microfluidic networks. PMID:22068594

  15. Effects of Crosslinking on the Mechanical Properties Drug Release, and Cytocompatibility of Protein Polymers

    PubMed Central

    Martinez, Adam W.; Caves, Jeffrey M.; Ravi, Swathi; Li, Wehnsheng; Chaikof, Elliot L.

    2013-01-01

    Recombinant elastin-like protein polymers are increasingly being investigated as component materials of a variety of implantable medical devices. This is chiefly a result of their favorable biological properties and the ability to tailor their physical and mechanical properties. In this report, we explore the potential of modulating the water content, mechanical properties, and drug release profiles of protein films through the selection of different crosslinking schemes and processing strategies. We find that the selection of crosslinking scheme and processing strategy has a significant influence on all aspects of protein polymer films. Significantly, utilization of a confined, fixed volume, as well as vapor phase crosslinking strategies decreased protein polymer equilibrium water content. Specifically, as compared to uncrosslinked protein gels, water content was reduced for genipin (15.5%), glutaraldehyde (GTA) (24.5%), GTA vapor crosslinking (31.6%), disulfide (SS) (18.2%), and SS vapor crosslinking (25.5%) (p <0.05). Distinct crosslinking strategies modulated protein polymer stiffness, strain at failure, and ultimate tensile strength (UTS). In all cases, vapor phase crosslinking produced the stiffest films with the highest UTS. Moreover, both confined, fixed volume and vapor phase approaches influenced drug delivery rates; with decreased initial drug burst and release rates as compared to solution phase crosslinking. Tailored crosslinking strategies provide an important option for modulating the physical, mechanical, and drug delivery properties of protein polymers. PMID:23993944

  16. Mechanophore activation in a crosslinked polymer matrix via instrumented indentation

    NASA Astrophysics Data System (ADS)

    Davis, Chelsea; Forster, Aaron; Woodcock, Jeremiah; Wang, Muzhou; Gilman, Jeffrey; Material Measurement Laboratory Team

    Recent advances in mechanically-activated fluorophores will enable a host of unique scientific challenges and opportunities to be addressed. Several mechanophores (MPs) in polymers have been reported, yet the specific deformation required to activate these molecules in a bulk polymer network has not been sufficiently specified. In an effort to develop the mechano-activation/deformation relationship of a spirolactam-based MP, scratches were applied to a MP-functionalized glassy crosslinked material at varying normal loads and lateral displacement rates. This experimental design allowed strain and strain rate effects to be decoupled. The fluorescence activation was then observed with a laser scanning confocal microscope. Areas of elastic and plastic deformation as well as brittle fracture were observed within each scratch as the normal loading of the indenter increased. The fluorescence intensity increased with increasing strain. Contact mechanics models are employed to demonstrate that relatively high degrees of strain are required to initiate the ring-opening activation transition within the spirolactam-based MP. These self-reporting damage sensors can be incorporated within polymeric coatings to allow real time structural health monitoring for a myriad of applications.

  17. Elucidation of the Cross-Link Structure of Nadic-End-Capped Polyimides Using NMR of C-13-Labeled Polymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Johnston, J. Christopher; Cavano, Paul J.

    1997-01-01

    Solid NMR of C-13 isotope-labeled samples of PMR-15 was used to follow the cross-linking reaction of the nadic end cap. Some samples were labeled on one of the carbon atoms of the nadic end cap, and others on the methylene carbon atom of the methylenedianiline portion of the polymer. NMR spectra were run on these samples both before and after cross-linking. In this way, direct evidence of the major products of cross-linking under normal cure conditions is provided. The majority (approximately 85%) of the cross-linking derives from olefin polymerization through the double bond of the end cap. Approximately 15% of the products could come from a pathway involving a retro-Diels-Alder reaction. However, all of the products could be explained by a biradical intermediate without a retro-Diels-Alder reaction. Evidence is also presented that the methylene moiety in the methylenedianiline part of the polymer chain also participates in the cross-linking, albeit to a small extent, by a radical transfer reaction. Different cure conditions (higher temperatures, longer times) could change the relative distribution of the products.

  18. 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

  19. Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

    1990-01-01

    A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

  20. A novel supramolecular polymer gel constructed by crosslinking pillar[5]arene-based supramolecular polymers through metal-ligand interactions.

    PubMed

    Wang, Pi; Xing, Hao; Xia, Danyu; Ji, Xiaofan

    2015-12-21

    A novel heteroditopic A-B monomer was synthesized and used to construct linear supramolecular polymers utilizing pillar[5]arene-based host-guest interactions. Specifically, upon addition of Cu(2+) ions, the supramolecular polymer chains are crosslinked through metal-ligand interactions, resulting in the formation of a supramolecular polymer gel. Interestingly, this self-organized supramolecular polymer can be used as a novel fluorescent sensor for detecting Cu(2+) ions. PMID:26466511

  1. 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.

  2. 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

  3. Gellan gum microspheres crosslinked with trivalent ion: effect of polymer and crosslinker concentrations on drug release and mucoadhesive properties.

    PubMed

    Boni, Fernanda Isadora; Prezotti, Fabíola Garavello; Cury, Beatriz Stringhetti Ferreira

    2016-08-01

    Gellan gum microspheres were obtained by ionotropic gelation technique, using the trivalent ion Al(3+). The percentage of entrapment efficiency ranged from 48.76 to 87.52% and 2(2) randomized full factorial design demonstrated that both the increase of polymer concentration and the decrease of crosslinker concentration presented a positive effect in the amount of encapsulated drug. Microspheres size and circularity ranged from 700.17 to 938.32 μm and from 0.641 to 0.796 μm, respectively. The increase of polymer concentration (1-2%) and crosslinker concentration (3-5%) led to the enlargement of particle size and circularity. However, the association of increased crosslinker concentration and reduced polymer content made the particles more irregular. In vitro and ex vivo tests evidenced the high mucoadhesiveness of microspheres. The high liquid uptake ability of the microspheres was demonstrated and the pH variation did not affect this parameter. Drug release was pH dependent, with low release rates in acid pH (42.40% and 44.93%) and a burst effect in phosphate buffer pH (7.4). The Weibull model had the best correlation with the drug release data, demonstrating that the release process was driven by a complex mechanism involving the erosion and swelling of the matrix or by non-Fickian diffusion. PMID:26616390

  4. Solid polymer electrolyte water electrolysis

    NASA Astrophysics Data System (ADS)

    Takenaka, H.; Torikai, E.; Kawami, Y.; Wakabayashi, N.

    Electrocatalyst performances and bonding to solid polymer electrolytes used for water electrolysis are investigated. Noble metal and metal alloy catalysts were plated to Nafion perfluorosulfonic acid polymer membranes without a binder by the use of a reducing agent solution held on the opposite side of the membrane from a metal salt solution. It was found that pretreatment of the membrane by hydrothermal treatment or gas plasma surface roughening improves metal adhesivity and thus reduces contact resistance between the membrane and the catalyst. Measurements of the constituents of cell voltage for platinum, rhodium and iridium anodes with platinum cathodes reveals that anodic overvoltage is a major component of voltage loss and depends on the type of electrocatalyst, being greatest for Pd and least for Ir. Ir and Ir-alloy electrodes, which were found to be the best catalysts for oxygen evolution, are found to have Tafel slopes of 0.04-0.06 V/decade. In a cell with a Pt cathode and Ir anode, cell voltage is observed to decrease with increasing temperature, reaching 1.56-1.59 V at a current density of 50 A/sq dm and 90 C, which corresponds to a thermal efficiency of 93-95%.

  5. ROMP-based thermosetting polymers from modified castor oil with various cross-linking agents

    NASA Astrophysics Data System (ADS)

    Ding, Rui

    Polymers derived from bio-renewable resources are finding an increase in global demand. In addition, polymers with distinctive functionalities are required in certain advanced fields, such as aerospace and civil engineering. In an attempt to meet both these needs, the goal of this work aims to develop a range of bio-based thermosetting matrix polymers for potential applications in multifunctional composites. Ring-opening metathesis polymerization (ROMP), which recently has been explored as a powerful method in polymer chemistry, was employed as a unique pathway to polymerize agricultural oil-based reactants. Specifically, a novel norbornyl-functionalized castor oil alcohol (NCA) was investigated to polymerize different cross-linking agents using ROMP. The effects of incorporating dicyclopentadiene (DCPD) and a norbornene-based crosslinker (CL) were systematically evaluated with respect to curing behavior and thermal mechanical properties of the polymers. Isothermal differential scanning calorimetry (DSC) was used to investigate the conversion during cure. Dynamic DSC scans at multiple heating rates revealed conversion-dependent activation energy by Ozawa-Flynn-Wall analysis. The glass transition temperature, storage modulus, and loss modulus for NCA/DCPD and NCA/CL copolymers with different cross-linking agent loading were compared using dynamic mechanical analysis. Cross-link density was examined to explain the very different dynamic mechanical behavior. Mechanical stress-strain curves were developed through tensile test, and thermal stability of the cross-linked polymers was evaluated by thermogravimetric analysis to further investigate the structure-property relationships in these systems.

  6. The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles.

    PubMed

    Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

    2015-10-28

    This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications. PMID:26416568

  7. The interplay of ion crosslinking, free ion content, and polymer mobility in PEO-based single-ion conductors

    NASA Astrophysics Data System (ADS)

    Lin, Kan-Ju; Maranas, Janna

    2010-03-01

    We use molecular dynamics simulation to study ion clustering and dynamics in ion containing polymers. This PEO based single-ion conducting ionomer serves as a model system for understanding cation transport in solid state polymer electrolytes (SPEs). Although small-angle x-ray scattering does not show an ionomer peak, we observer various cation-anion complexes in the simulation, suggesting ionomer backbones are crosslinked through ion complexes. These crosslinks reduce the adjacent PEO mobility resulting in a symmetric mobility gradient along the PEO chain. We vary the cation-anion interaction in the simulation to observe the interplay of cation-anion association, polymer mobility and cation motion. Cation-anion association controls the number of free ions, which is important in ionic conductivity when these materials are used as SPEs. Polymer mobility controls how fast the free ions are able to move through the SPE. High conductivity requires both a high free ion content and fast polymer motion. To understand the connection between the two, we ``tune'' the force field in order to manipulate the free ion content and observe the influence on PEO dynamics.

  8. Investigation of anisotropic thermal transport in cross-linked polymers

    NASA Astrophysics Data System (ADS)

    Simavilla, David Nieto

    Thermal transport in lightly cross-linked polyisoprene and polybutadine subjected to uniaxial elongation is investigated experimentally. We employ two experimental techniques to assess the effect that deformation has on this class of materials. The first technique, which is based on Forced Rayleigh Scattering (FRS), allows us to measure the two independent components of the thermal diffusivity tensor as a function of deformation. These measurements along with independent measurements of the tensile stress and birefringence are used to evaluate the stress-thermal and stress-optic rules. The stress-thermal rule is found to be valid for the entire range of elongations applied. In contrast, the stress-optic rule fails for moderate to large stretch ratios. This suggests that the degree of anisotropy in thermal conductivity depends on both orientation and tension in polymer chain segments. The second technique, which is based on infrared thermography (IRT), allows us to measure anisotropy in thermal conductivity and strain induced changes in heat capacity. We validate this method measurements of anisotropic thermal conductivity by comparing them with those obtained using FRS. We find excellent agreement between the two techniques. Uncertainty in the infrared thermography method measurements is estimated to be about 2-5 %. The accuracy of the method and its potential application to non-transparent materials makes it a good alternative to extend current research on anisotropic thermal transport in polymeric materials. A second IRT application allows us to investigate the dependence of heat capacity on deformation. We find that heat capacity increases with stretch ratio in polyisoprene specimens under uniaxial extension. The deviation from the equilibrium value of heat capacity is consistent with an independent set of experiments comparing anisotropy in thermal diffusivity and conductivity employing FRS and IRT techniques. We identify finite extensibility and strain

  9. Mechanochromism and Mechanical-Force-Triggered Cross-Linking from a Single Reactive Moiety Incorporated into Polymer Chains.

    PubMed

    Zhang, Huan; Gao, Fei; Cao, Xiaodong; Li, Yanqun; Xu, Yuanze; Weng, Wengui; Boulatov, Roman

    2016-02-01

    Incorporation of small reactive moieties, the reactivity of which depends on externally imposed load (so-called mechanophores) into polymer chains offers access to a broad range of stress-responsive materials. Here, we report that polymers incorporating spirothiopyran (STP) manifest both green mechanochromism and load-induced addition reactions in solution and solid. Stretching a macromolecule containing colorless STP converts it into green thiomerocyanine (TMC), the mechanically activated thiolate moiety of which undergoes rapid thiol-ene click reactions with certain reactive C=C bonds to form a graft or a cross-link. The unique dual mechanochemical response of STP makes it of potentially great utility both for the design of new stress-responsive materials and for fundamental studies in polymer physics, for example, the dynamics of physical and mechanochemical remodeling of loaded materials. PMID:26805709

  10. Polymer Composition and Substrate Influences on the Adhesive Bonding of a Biomimetic, Cross-Linking Polymer

    PubMed Central

    Matos-Pérez, Cristina R.; White, James D.; Wilker, Jonathan J.

    2012-01-01

    Hierarchical biological materials such as bone, sea shells, and marine bioadhesives are providing inspiration for the assembly of synthetic molecules into complex structures. The adhesive system of marine mussels has been the focus of much attention in recent years. Several catechol-containing polymers are being developed to mimic the cross-linking of proteins containing 3,4-dihydroxyphenylalanine (DOPA) used by shellfish for sticking to rocks. Many of these biomimetic polymer systems have been shown to form surface coatings or hydrogels, however bulk adhesion is demonstrated less often. Developing adhesives requires addressing design issues including finding a good balance between cohesive and adhesive bonding interactions. Despite the growing number of mussel mimicking polymers, there has been little effort to generate structure-property relations and gain insights on what chemical traits give rise to the best glues. In this report, we examined the simplest of these biomimetic polymers, poly[(3,4-dihydroxystyrene)-co-styrene]. Pendant catechol groups (i.e., 3,4-dihydroxystyrene) were distributed throughout a polystyrene backbone. Several polymer derivatives were prepared, each with a different 3,4-dihyroxystyrene content. Bulk adhesion testing showed where the optimal middle ground of cohesive and adhesive bonding resides. Adhesive performance was benchmarked against commercial glues as well as the genuine material produced by live mussels. In the best case, bonding was similar to cyanoacrylate “Krazy” or “Super” glue. Performance was also examined using low (e.g., plastics) and high (e.g., metals, wood) energy surfaces. Adhesive bonding of poly[(3,4-dihydroxystyrene)-co-styrene] may be the strongest of reported mussel protein mimics. These insights should help us to design future biomimetic systems, thereby bringing us closer to development of bone cements, dental composites, and surgical glues. PMID:22582754

  11. Polymer composition and substrate influences on the adhesive bonding of a biomimetic, cross-linking polymer.

    PubMed

    Matos-Pérez, Cristina R; White, James D; Wilker, Jonathan J

    2012-06-01

    Hierarchical biological materials such as bone, sea shells, and marine bioadhesives are providing inspiration for the assembly of synthetic molecules into complex structures. The adhesive system of marine mussels has been the focus of much attention in recent years. Several catechol-containing polymers are being developed to mimic the cross-linking of proteins containing 3,4-dihydroxyphenylalanine (DOPA) used by shellfish for sticking to rocks. Many of these biomimetic polymer systems have been shown to form surface coatings or hydrogels; however, bulk adhesion is demonstrated less often. Developing adhesives requires addressing design issues including finding a good balance between cohesive and adhesive bonding interactions. Despite the growing number of mussel-mimicking polymers, there has been little effort to generate structure-property relations and gain insights on what chemical traits give rise to the best glues. In this report, we examine the simplest of these biomimetic polymers, poly[(3,4-dihydroxystyrene)-co-styrene]. Pendant catechol groups (i.e., 3,4-dihydroxystyrene) are distributed throughout a polystyrene backbone. Several polymer derivatives were prepared, each with a different 3,4-dihyroxystyrene content. Bulk adhesion testing showed where the optimal middle ground of cohesive and adhesive bonding resides. Adhesive performance was benchmarked against commercial glues as well as the genuine material produced by live mussels. In the best case, bonding was similar to that obtained with cyanoacrylate "Krazy Glue". Performance was also examined using low- (e.g., plastics) and high-energy (e.g., metals, wood) surfaces. The adhesive bonding of poly[(3,4-dihydroxystyrene)-co-styrene] may be the strongest of reported mussel protein mimics. These insights should help us to design future biomimetic systems, thereby bringing us closer to development of bone cements, dental composites, and surgical glues. PMID:22582754

  12. Strain Hardening and Strain Softening of Reversibly Cross-linked Supramolecular Polymer Networks

    PubMed Central

    Xu, Donghua; Craig, Stephen L.

    2011-01-01

    The large amplitude oscillatory shear behavior of metallo-supramolecular polymer networks formed by adding bis-Pd(II) cross-linkers to poly(4-vinylpyridine) (PVP) in dimethyl sulfoxide (DMSO) solution is reported. The influence of scanning frequency, dissociation rate of cross-linkers, concentration of cross-linkers, and concentration of PVP solution on the large amplitude oscillatory shear behavior is explored. In semidilute unentangled PVP solutions, above a critical scanning frequency, strain hardening of both storage moduli and loss moduli is observed. In the semidilute entangled regime of PVP solution, however, strain softening is observed for samples with faster cross-linkers (kd ∼ 1450 s−1), whereas strain hardening is observed for samples with slower cross-linkers (kd ∼ 17 s−1). The mechanism of strain hardening is attributed primarily to a strain-induced increase in the number of elastically active chains, with possible contributions from non-Gaussian stretching of polymer chains at strains approaching network fracture. The divergent strain softening of samples with faster cross-linkers in semidilute entangled PVP solutions, relative to the strain hardening of samples with slower cross-linkers, is consistent with observed shear thinning/shear thickening behavior reported previously and is attributed to the fact that the average time that a cross-linker remains detached is too short to permit the local relaxation of polymer chain segments that is necessary for a net conversion of elastically inactive to elastically active cross-linkers. These and other observations paint a picture in which strain softening and shear thinning arise from the same set of molecular mechanisms, conceptually uniting the two nonlinear responses for this system. PMID:22043083

  13. Photo-induced in situ crosslinking of polymer brushes with dimethyl maleimide moieties for dynamically stimulating stem cell differentiation.

    PubMed

    Arisaka, Yoshinori; Nishijima, Yuka; Yusa, Shin-Ichi; Takeda, Naoya

    2016-09-01

    We designed photo-crosslinkable polymer brushes with dimethylmaleimide moieties, in order to demonstrate dynamic stimulation of cell differentiation in mesenchymal stem cells (MSCs). The polymer brushes were synthesized by surface-initiated reversible addition fragmentation chain transfer polymerization using dimethylmaleimide ethyl methacrylate and methyl methacrylate on a chain transfer agent-immobilized glass surface. The polymer brushes were crosslinked by photodimerization of the dimethylmaleimide moieties within polymer chains with stem cells present on the surface. In order to evaluate the effects of in situ photo-induced crosslinking of the polymer brushes on gene expression of stem cells, human bone marrow MSCs were cultured under static and dynamic culture conditions for 7 days. Expression of the osteocalcin (Ocn) gene in MSCs was used as an indicator of osteoblast differentiation under dynamic culture conditions. Structural conversion from non-crosslinked polymer brushes to crosslinked polymer brushes increased the expression of Ocn by 1.4-fold in the presence of adhered cells, compared with non-crosslinked polymer brushes under static culture conditions. These results suggest that MSCs recognized surface conversion from non-crosslinked to crosslinked structures, which resulted in altered differentiation lineages. Therefore, photo-crosslinkable surfaces with dimethyl maleimide moieties are potential novel materials for dynamically stimulating MSC differentiation. PMID:27255343

  14. 3D Mapping of Polymer Crosslink Density with Magnetic Resonance Imaging

    SciTech Connect

    Herberg, J L; Gjersing, E L; Chinn, S C; Maxwell, R S

    2005-03-11

    Magnetic Resonance Imaging (MRI) techniques have been used to detect areas of low crosslink density in damaged silicone parts in an effort to develop a QA/QC protocol to be used in the development of new parts. Model materials of varying crosslink density first demonstrated the applicability of the method. Analysis of damaged pads has been shown to be clearly distinguishable by MRI. It is our belief that both the T{sub 2} weighted SPI NMR and the T{sub 2} weighted water/fat suppression MRI experiments can be used to map out the location of different cross-linking densities, ultimately determining the quality or homogeneity in polymers.

  15. 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

  16. 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

  17. Predicting the glass transition temperature as function of crosslink density and polymer interactions in rubber compounds

    NASA Astrophysics Data System (ADS)

    D'Escamard, Gabriella; De Rosa, Claudio; Auriemma, Finizia

    2016-05-01

    Crosslink sulfur density in rubber compounds and interactions in polymer blends are two of the composition elements that affect the rubber compound properties and glass transition temperature (Tg), which is a marker of polymer properties related to its applications. Natural rubber (NR), butadiene rubber (BR) and styrene-butadiene rubber (SBR) compounds were investigated using calorimetry (DSC) and dynamic mechanical analysis (DMA). The results indicate that the Di Marzio's and Schneider's Models predict with accuracy the dependence of Tg on crosslink density and composition in miscible blends, respectively, and that the two model may represent the base to study the relevant "in service" properties of real rubber compounds.

  18. Modification of biodegradable polymers by radiation crosslinking technique with polyfunctional monomers

    NASA Astrophysics Data System (ADS)

    Yoshii, Fumio; Suhartini, Meri; Nagasawa, Naotsugu; Mitomo, Hiroshi; Kume, Tamikazu

    2003-08-01

    Poly(ɛ-caprolactone) (PCL) and poly(butylene succinate-co-adipate) (PBSA) were electron beam-irradiated in the presence of five different polyfunctional monomers at ambient temperature. Trimethallyl isocyanurate (TMAIC) has been found to greatly enhance the radiation crosslinking of PCL and PBSA. It was pointed out that the optimum yield of gel fraction can be achieved when the polymers were irradiated at a dose of 50 kGy in the presence of 1% TMAIC. High gel fraction largely improves heat stability of PBSA, while biodegradability evaluated by soil burial test of the crosslinked polymers is slightly retarded, however they are effectively destroyed with a slightly smaller rate.

  19. Electron Beam Crosslinked Polyurethane Shape Memory Polymers with Tunable Mechanical Properties

    PubMed Central

    Hearon, Keith; Nash, Landon D.; Volk, Brent L.; Ware, Taylor; Lewicki, James P.; Voit, Walter E.; Wilson, Thomas S.

    2014-01-01

    Novel electron beam crosslinked polyurethane shape memory polymers with advanced processing capabilities and tunable thermomechanical properties have been synthesized and characterized. We demonstrate the ability to manipulate crosslink density in order to finely tune rubbery modulus, strain capacity, ultimate tensile strength, recovery stress, and glass transition temperature. This objective is accomplished for the first time in a low-molecular-weight polymer system through the precise engineering of thermoplastic resin precursors suitable for mass thermoplastic processing. Neurovascular stent prototypes were fabricated by dip-coating and laser machining to demonstrate processability. PMID:25411531

  20. In situ Synthesis of Oligonucleotide Arrays on Surfaces Coated with Crosslinked Polymer Multilayers.

    PubMed

    Broderick, Adam H; Lockett, Matthew R; Buck, Maren E; Yuan, Yuan; Smith, Lloyd M; Lynn, David M

    2012-03-13

    We report an approach to the in situ synthesis of oligonucleotide arrays on surfaces coated with crosslinked polymer multilayers. Our approach makes use of methods for the 'reactive' layer-by-layer assembly of thin, amine-reactive multilayers using branched polyethyleneimine (PEI) and the azlactone-functionalized polymer poly(2-vinyl-4,4'-dimethylazlactone) (PVDMA). Post-fabrication treatment of film-coated glass substrates with d-glucamine or 4-amino-1-butanol yielded hydroxyl-functionalized films suitable for the Maskless Array Synthesis (MAS) of oligonucleotide arrays. Glucamine-functionalized films yielded arrays of oligonucleotides with fluorescence intensities and signal-to-noise ratios (after hybridization with fluorescently labeled complementary strands) comparable to those of arrays fabricated on conventional silanized glass substrates. These arrays could be exposed to multiple hybridization-dehybridization cycles with only moderate loss of hybridization density. The versatility of the layer-by-layer approach also permitted synthesis directly on thin sheets of film-coated poly(ethylene terephthalate) (PET) to yield flexible oligonucleotide arrays that could be readily manipulated (e.g., bent) and cut into smaller arrays. To our knowledge, this work presents the first use of polymer multilayers as a substrate for the multi-step synthesis of complex molecules. Our results demonstrate that these films are robust and able to withstand the ~450 individual chemical processing steps associated with MAS (as well as manipulations required to hybridize, image, and dehybridize the arrays) without large-scale cracking, peeling, or delamination of the thin films. The combination of layer-by-layer assembly and MAS provides a means of fabricating functional oligonucleotide arrays on a range of different materials and substrates. This approach may also prove useful for the fabrication of supports for the solid-phase synthesis and screening of other macromolecular or small

  1. Surface morphology control of cross-linked polymer particles via dispersion polymerization.

    PubMed

    Peng, Bo; Imhof, Arnout

    2015-05-14

    Cross-linked polymer colloids (poly(methyl methacrylate) and polystyrene) with diverse shapes were prepared in polar solvents (ethanol, methanol and water) via dispersion polymerization, in which a linear addition of the cross-linker was used during reaction. Apart from spherical particles we found dented spheres or particles covered with nodules, or a combination of both. A comprehensive investigation was carried out, mainly concentrating on the effect of the experimental conditions (e.g., the addition start time and total addition time, cross-linker density and the solvency of the solvents) on particle morphologies. Consequently, we suggest a number of effective ways for the synthesis of regular (spherical) colloidal particles through maintaining a relatively low concentration of the cross-linker during the entire reaction, or forcing the co-polymerization (of monomer and cross-linker) locus to the continuous medium, or using a high quality or quantity of the stabilizer. Moreover, the size of the particles was also precisely manipulated by varying the polarity of the solvents, the concentration of the cross-linker, and the amount and average molecular weight of the stabilizer. In addition, the formation of the heavily dented particles with a very rough surface prepared under a pure or oxygen-'contaminated' nitrogen environment was monitored over time. The results accumulated in this article are of use for a better understanding of the mechanism of the polymerization and control over the structure and property of polymer particles. PMID:25793973

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

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

    2007-01-01

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

  3. The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

    2015-10-01

    This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the

  4. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity.

    PubMed

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-01-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies. PMID:26677949

  5. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

    NASA Astrophysics Data System (ADS)

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-12-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

  6. Removal of Parabens from Aqueous Solution Using β-Cyclodextrin Cross-Linked Polymer

    PubMed Central

    Chin, Yuk Ping; Mohamad, Sharifah; Abas, Mhd Radzi Bin

    2010-01-01

    The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results. PMID:20957106

  7. Removal of parabens from aqueous solution using β-cyclodextrin cross-linked polymer.

    PubMed

    Chin, Yuk Ping; Mohamad, Sharifah; Abas, Mhd Radzi Bin

    2010-01-01

    The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results. PMID:20957106

  8. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

    PubMed Central

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-01-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies. PMID:26677949

  9. Biodegradable Photo-Crosslinked Thin Polymer Networks Based on Vegetable Oil Hydroxyfatty Acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Novel crosslinked thin polymer networks based on vegetable oil hydroxyfatty acids (HFAs) were prepared by UV photopolymerization and their mechanical properties were evaluated. Two raw materials, castor oil and 7,10-dihydroxy-8(E)-octadecenoic acid (DOD) were used as sources of mono- and di-HFAs, r...

  10. Direct Patterning of Organic Functional Polymers through Conventional Photolithography and Noninvasive Cross-Link Agents.

    PubMed

    Squillaci, Marco A; Qiu, Feng; Aliprandi, Alessandro; Zhang, Fan; Feng, Xinliang; Samorì, Paolo

    2016-07-01

    A new technique for direct patterning of functional organic polymers using commercial photolithography setups with a minimal loss of the materials' performances is reported. This result is achieved through novel cross-link agents made by boron- and fluorine-containing heterocycles that can react between themselves upon UV- and white-light exposure. PMID:27153351

  11. Influence of radiation-crosslinking on flame retarded polymer materials-How crosslinking disrupts the barrier effect

    NASA Astrophysics Data System (ADS)

    Sonnier, Rodolphe; Caro-Bretelle, Anne-Sophie; Dumazert, Loïc; Longerey, Marc; Otazaghine, Belkacem

    2015-01-01

    Fire behavior of flame retardant-free and flame retarded PP/PA6 blends was studied using pyrolysis-combustion flow calorimeter, cone calorimeter and epiradiator equipped with infrared camera and pyrometer. Blends were previously γ-irradiated in presence of crosslinking agents at various doses (up to 100 kGy) in order to assess the influence of irradiation crosslinking on flame retardancy. Crosslinked specimens exhibit a solid-like behavior under high temperature gradient in cone calorimeter and then distort considerably. The influence of such a behavior depends on the material properties. When the flame retardancy is provided by heat shielding effect, heat distortion disrupts the top protective layer leading to a substantial increase of peak of heat release rate (pHRR). The barrier layer is no longer able to prevent the heat transfer to the underlying condensed phase. In other cases (flame retardant-free blends or flame retardancy provided by other effects than heat shielding), heat distortion has negligible influence on heat release rate curves in cone calorimeter tests.

  12. 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.

  13. Evaluation of a cross-linked polyurethane acrylate as polymer electrolyte for lithium batteries

    SciTech Connect

    Santhosh, P.; Gopalan, A. . E-mail: algopal_99@yahoo.com; Vasudevan, T.; Lee, Kwang-Pill

    2006-06-15

    A cross-linked polyurethane acrylate (CL-PUA) was synthesized by end capping 2,6-toluene diisocyanate (TDI)/poly(ethylene glycol) (PEG) based prepolymer with hydroxybutyl methacrylate (HBMA). Differential scanning calorimetry (DSC) and Fourier transform infra-red (FT-IR) spectroscopy measurements reveal the possible presence of significant interactions between lithium ions and soft/hard segments of the CL-PUA, when CL-PUA was complexed with lithium perchlorate (LiClO{sub 4}). CL-PUA follows the VTF relationship for the ion transport. Predominant formation of contact ion pairs of LiClO{sub 4} has been observed through AC conductivity and DSC measurements. The lithium stripping-plating process is a reversible and implies better electrochemical stability in the working voltage range. Also, CL-PUA electrolyte shows better compatibility with lithium metal as inferred from impedance measurements and has a good cationic transference number suitable to be used as a solid polymer electrolyte. The addition of HBMA into PU matrix improves tensile strength of the CL-PUA. Swelling measurements of CL-PUA with plasticizer showed better dimensional stability. Also, a cell was constructed using CL-PUA as electrolyte and the performance was assessed.

  14. Stress-Strain Relation of Tire Rubber Consist of Entangled Polymers, Fillers and Crosslink

    NASA Astrophysics Data System (ADS)

    Hagita, Katsumi; Bito, Y.; Minagawa, Y.; Omiya, M.; Morita, H.; Doi, M.; Takano, H.

    2009-03-01

    We presented a preliminary result of large scale coarse-grained Molecular Dynamics simulation of filled polymer melts with Sulfur-crosslink under an uni-axial deformation by using the Kremer-Grest Model. The size of simulation box under periodic boundary conditions (PBC) is set to about 66nm to consider length of entangled polymer chains, size and structure of fillers, and non-uniform distribution of crosslink. We put 640 polymer chains of 1024 particles and 32 fillers into the PBC box. Each filler consists of 1280 particles of the C1280 fullerene structure. A repulsive force from the center of the filler is applied to the particles. Here, the particles of the fillers are chosen to be the same as the particles of the polymers and the diameter of the filler is about 15nm. The distribution of the fillers used in this simulation is provided by the result of 2d pattern RMC analysis for 2D-USAXS experiments at SPring-8. Sulfur crosslink are randomly distributed in the system. It is found that stress-strain curves estimated by applying a certain uni-axial deformation to the system in simulations are in good agreement with those in experiments. It is successful to show difference on the S-S curve between existence / absence of fillers and qualitative dependence of attractive force between polymer and filler.

  15. Preparation and Characterization of a pH-Responsive Core Cross-linked Polymer Micelle

    NASA Astrophysics Data System (ADS)

    Kousaka, Shouta; Sugahara, Makoto; Endo, Tatsuya; Yusa, Shin-ichi

    2011-01-01

    Poly(ethylene glycol)-b-poly(2-(diethylamino) ethyl methacrylate-co-2-cinnamoyl-oxyethyl acrylate) (PEG-b-P(DEA/CEA)) was prepared by reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization. pH-responsive association behaviour of PEG-b-P(DEA/CEA) in 0.1 M NaCl was characterized by dynamic light scattering (DLS). As solution pH is increased from an acidic pH, the hydrodynamic radius (Rh) increases, indicative of the polymer micelle formation. The formation of a micelle was also supported by static light scattering (SLS) data. The cinnamoyl groups in the core of the polymer micelle undergo photodimerization, yielding cross-links between polymer chains. The core of the polymer micelle was fixed, which was confirmed by DLS, SLS, and small angle X-ray scattering (SAXS) techniques. When pH is decreased to 3, Rh of the core cross-linked (CCL) polymer micelle slightly increases due to the protonation of the DEA unit in the cross-linked core. The reversible pH-induced swelling and shrinking behaviour can be observed.

  16. Order-Disorder Transitions in Cross-Linked Block Copolymer Solids

    SciTech Connect

    Das, J.

    2005-01-12

    With a view toward creating solid block copolymers wherein the order-disorder transition can be accessed many times they investigated the nature of order-disorder transitions in cross-linked diblock copolymer melts using synergistic theory and experiment. A mean-field theory based on a coarse grained free-energy and the Random Phase Approximation (RPA) is developed for the system of interest. The quenched distribution of cross-links is averaged using the replica method. The phase behavior of a particular A-B block copolymer melt with a randomly cross-linked B-Block is determined as a function of the Florry-Huggins interaction parameter ({chi}) and the average number of cross-links per chain N{sub c}. They find for a cross-link density greater than N*{sub c} the B monomers are localized within a region of size {zeta} {approx} (N{sub c} - N*{sub c}){sup -1/2}. The cross-links strongly oppose ordering in the system as {zeta} becomes comparable to the radius of gyration of the block copolymer chain. As such the order-disorder transition temperature T{sub ODT} decreases precipitously when N{sub c} > N*{sub c}. When N{sub c} < N*{sub c}, T{sub ODT} increases weakly with N{sub c}. Experiments were conducted on cross-linked polystyrene-block-polyisoprene copolymer samples wherein the polyisoprene block was selectively cross-linked at a temperature well above the order-disorder transition temperature of the pure block copolymer. Small angle X-ray scattering (SAXS) and birefringence measurements on the cross-linked samples are consistent with the theoretical prediction. T{sub ODT} decreases rapidly when the cross-linking density exceeds the critical cross-linking density.

  17. Computational exploration of polymer nanocomposite mechanical property modification via cross-linking topology

    SciTech Connect

    Lacevic, N; Gee, R; Saab, A; Maxwell, R

    2008-04-24

    Molecular dynamics simulations have been performed in order to study the effects of nanoscale filler cross-linking topologies and loading levels on the mechanical properties of a model elastomeric nanocomposite. The model system considered here is constructed from octa-functional polyhedral oligomeric silsesquioxane (POSS) dispersed in a poly(dimethylsiloxane) (PDMS) matrix. Shear moduli, G, have been computed for pure and for filled and unfilled PDMS as a function of cross-linking density, POSS fill loading level, and polymer network topology. The results reported here show that G increases as the cross-linking (covalent bonds formed between the POSS and the PDMS network) density increases. Further, G is found to have a strong dependence on cross-linking topology. The increase in shear modulus, G, for POSS filled PDMS is significantly higher than that for unfilled PDMS cross-linked with standard molecular species, suggesting an enhanced reinforcement mechanism for POSS. In contrast, in blended systems (POSS/PDMS mixture with no cross-linking) G was not observed to significantly increase with POSS loading. Finally, we find intriguing differences in the structural arrangement of bond strains between the cross-linked and the blended systems. In the unfilled PDMS the distribution of highly strained bonds appears to be random, while in the POSS filled system, the strained bonds form a net-like distribution that spans the network. Such a distribution may form a structural network 'holding' the composite together and resulting in increases in G compared to an unfilled, cross-linked system. These results are of importance for engineering of new POSS-based multifunctional materials with tailor-made mechanical properties.

  18. Polymer Micelles with Cross-Linked Polyanion Core for Delivery of a Cationic Drug Doxorubicin

    PubMed Central

    Kim, Jong Oh; Kabanov, Alexander V.; Bronich, Tatiana K.

    2009-01-01

    Polymer micelles with cross-linked ionic cores were prepared by using block ionomer complexes of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMA) copolymer and divalent metal cations as templates. Doxorubicin (DOX), an anthracycline anticancer drug, was successfully incorporated into the ionic cores of such micelles via electrostatic interactions. A substantial drug loading level (up to 50 w/w %) was achieved and it was strongly dependent on the structure of the cross-linked micelles and pH. The drug-loaded micelles were stable in aqueous dispersions exhibiting no aggregation or precipitation for a prolonged period of time. The DOX-loaded polymer micelles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment due to the protonation of carboxylic groups in the cores of the micelles. The attempt to protect the DOX-loaded core with the polycationic substances resulted in the decrease of loading efficacy and had a slight effect on the release characteristics of the micelles. The DOX-loaded polymer micelles exhibited a potent cytotoxicity against human A2780 ovarian carcinoma cells. These results point to a potential of novel polymer micelles with cross-linked ionic cores to be attractive carriers for the delivery of DOX. PMID:19386272

  19. Cross-Linked Nanoporous Materials from Reactive and Multifunctional Block Polymers

    SciTech Connect

    Seo, Myungeun; Amendt, Mark A.; Hillmyer, Marc A.

    2012-10-10

    Polylactide-b-poly(styrene-co-2-hydroxyethylmethacrylate) (PLA-b-P(S-co-HEMA)) and polylactide-b-poly(styrene-co-2-hydroxyethylacrylate) (PLA-b-P(S-co-HEA)) were synthesized by combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization. {sup 1}H nuclear magnetic resonance spectroscopy and size exclusion chromatography data indicated that the polymerizations were controlled and that hydroxyl groups were successfully incorporated into the block polymers. The polymers were reacted with 4,4{prime}-methylenebis(phenyl isocyanate) (MDI) to form the corresponding cross-linked materials. The materials were annealed at 150 C to complete the coupling reaction. Robust nanoporous materials were obtained from the cross-linked polymers by treatment with aqueous base to hydrolyze the PLA phase. Small-angle X-ray scattering study combined with scanning electron microscopy showed that MDI-cross-linked PLA-b-P(S-co-HEMA)/PLA-b-P(S-co-HEA) can adopt lamellar, hexagonally perforated lamellar, and hexagonally packed cylindrical morphologies after annealing. In particular, the HPL morphology was found to evolve from lamellae due to increase in volume fraction of PS phase as MDI reacted with hydroxyl groups. The reaction also kinetically trapped the morphology by cross-linking. Bicontinuous morphologies were also observed when dibutyltin dilaurate was added to accelerate reaction between the polymer and MDI.

  20. Amino resins crosslinked polymer gels for permeability profile control

    SciTech Connect

    Shu, P.

    1989-05-30

    This patent describes a process for closing pores in a hydrocarbonaceous fluid bearing formation to obtain improved sweep efficiency during a waterflood oil recovery operation which comprises injecting a gellable composition comprising: (a) water; (b) 0.2 to 5.0 wt. percent of a cross linkable polymer which is a member selected from the group consisting of xanthan biopolymers, heteropolysaccharide S-130, poly (acrylamide-co-acrylamido-2-methyl-propanesulfonate), and acrylamide modified polyvinyl alcohol; and (c) 0.02 to 50.0 wt. percent of a partially methylated aminoplast resin which cross links with the polymer thereby forming a gel in the absence of a salt which is acid generating upon the application of heat which gel is of a strength sufficient to close pores in one or more permeable zones of the formation.

  1. 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

  2. Morphology control in solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Li, Christopher

    2015-03-01

    Solid polymer electrolytes (SPEs) with high ionic conductivity are important for energy-related applications, such as solid state batteries and fuel cells. In this talk, I will discuss how nanoscale morphology affects the properties of SPEs. In the first part of the talk, I will show quantitatively that the effect of polymer crystallization on ion transport is twofold: structural (tortuosity) and dynamic (tethered chain confinement). We decouple these two effects by designing and fabricating a model polymer single crystal electrolyte system with controlled crystal structure, size, crystallinity, and orientation. Ion conduction is confined within the chain fold region and guided by the crystalline lamellae. We show that, at low ion content, due to the tortuosity effect, the in-plane conductivity is 2000 times greater than through-plane one. Contradictory to the general view, the dynamic effect is negligible at moderate ion contents. Our results suggest that semicrystalline polymer is a valid system for practical polymer electrolytes design. In the second part of the talk, I will discuss how to use holographic photopolymerization (HP) to fabricate long-range, defect-free, ordered SPEs with tunable ion conducting pathways. By incorporating polymer electrolytes into the carefully selected HP system, electrolyte layers/ion channels with length scales of a few tens of nanometers to micrometers can be formed. Confinement effects on ion transport will be reported.

  3. Multi-stimulus-responsive shape-memory polymer nanocomposite network cross-linked by cellulose nanocrystals.

    PubMed

    Liu, Ye; Li, Ying; Yang, Guang; Zheng, Xiaotong; Zhou, Shaobing

    2015-02-25

    In this study, we developed a thermoresponsive and water-responsive shape-memory polymer nanocomposite network by chemically cross-linking cellulose nanocrystals (CNCs) with polycaprolactone (PCL) and polyethylene glycol (PEG). The nanocomposite network was fully characterized, including the microstructure, cross-link density, water contact angle, water uptake, crystallinity, thermal properties, and static and dynamic mechanical properties. We found that the PEG[60]-PCL[40]-CNC[10] nanocomposite exhibited excellent thermo-induced and water-induced shape-memory effects in water at 37 °C (close to body temperature), and the introduction of CNC clearly improved the mechanical properties of the mixture of both PEG and PCL polymers with low molecular weights. In addition, Alamar blue assays based on osteoblasts indicated that the nanocomposites possessed good cytocompatibility. Therefore, this thermoresponsive and water-responsive shape-memory nanocomposite could be potentially developed into a new smart biomaterial. PMID:25647407

  4. 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.

  5. Cross-linked supramolecular polymer metallogels constructed via a self-sorting strategy and their multiple stimulus-response behaviors.

    PubMed

    Wang, Xu-Qing; Wang, Wei; Yin, Guang-Qiang; Wang, Yu-Xuan; Zhang, Chang-Wei; Shi, Jia-Meng; Yu, Yihua; Yang, Hai-Bo

    2015-12-01

    Novel cross-linked supramolecular polymer metallogels were successfully constructed from four components via a self-sorting strategy, and feature interesting multiple stimulus-response behaviors under various external stimuli, including halide, base, and competitive guests. PMID:26436148

  6. Effects of sensitizer length on radiation crosslinked shape-memory polymers

    NASA Astrophysics Data System (ADS)

    Ware, Taylor; Voit, Walter; Gall, Ken

    2010-04-01

    Shape-memory polymers (SMPs) are smart materials that can be designed to retain a metastable state and upon activation, recover a preprogrammed shape. In this study, poly(methyl acrylate) (PMA) is blended with poly(ethylene glycol) diacrylate (PEGDA) of various molecular weights in various concentrations and subsequently exposed to ionizing radiation. PEGDA sensitizes the radiation crosslinking of PMA, lowering the minimum absorbed dose for gelation and increasing the rubbery modulus, after crosslinking. Minimum dose for gelation, as determined by the Charlesby-Pinner equation, decreases from 25.57 kGy for unblended PMA to 2.06 kGy for PMA blended with 10.00 mole% PEGDA. Moreover, increase in the blend concentration of PEGDA increases the crosslinking density of the resulting networks. Sensitizer length, namely Mn of PEGDA, also affects crosslinking and final mechanical properties. Increase in the length of the PEGDA molecule at a constant molar ratio increases the efficacy of the molecule as a radiation sensitizer as determined by the increase in gel fraction and rubbery modulus across doses. However, at a constant weight ratio of PEGDA to PMA, shorter PEGDA chains sensitize more crosslinking because they have more reactive ends per weight fraction. Sensitized samples of PMA with PEGDA were tested for shape-memory properties and showed shape fixity of greater than 99%. Samples had a glass transition temperature near 28 °C and recovered between 97% and 99% of the induced strain when strained to 50%.

  7. Effective-medium approach for stiff polymer networks with flexible cross-links

    NASA Astrophysics Data System (ADS)

    Broedersz, C. P.; Storm, C.; Mackintosh, F. C.

    2009-06-01

    Recent experiments have demonstrated that the nonlinear elasticity of in vitro networks of the biopolymer actin is dramatically altered in the presence of a flexible cross-linker such as the abundant cytoskeletal protein filamin. The basic principles of such networks remain poorly understood. Here we describe an effective-medium theory of flexibly cross-linked stiff polymer networks. We argue that the response of the cross-links can be fully attributed to entropic stiffening, while softening due to domain unfolding can be ignored. The network is modeled as a collection of randomly oriented rods connected by flexible cross-links to an elastic continuum. This effective medium is treated in a linear elastic limit as well as in a more general framework, in which the medium self-consistently represents the nonlinear network behavior. This model predicts that the nonlinear elastic response sets in at strains proportional to cross-linker length and inversely proportional to filament length. Furthermore, we find that the differential modulus scales linearly with the stress in the stiffening regime. These results are in excellent agreement with bulk rheology data.

  8. Mechanochemically induced disordered structures of vincamine: the different mediation of two cross-linked polymers.

    PubMed

    Hasa, Dritan; Perissutti, Beatrice; Chierotti, Michele Remo; Gobetto, Roberto; Grabnar, Iztok; Bonifacio, Alois; Dall'Acqua, Stefano; Invernizzi, Sergio; Voinovich, Dario

    2012-10-15

    The aims of this research were to prepare highly bioavailable binary cogrounds (vincamine-AcDiSol(®) or PVP-Cl) by means of a mechanochemical process and to study the mediation of each polymer in the induction of physical transformations of the drug. From a set of fifteen cogrounds for each crosslinked polymer, two samples were selected in each group on the basis of the AUC of in vitro dissolution profiles with the help of a statistical comparison. The chosen samples were analysed by means of TEM, XRPD, Raman-spectroscopy/imaging, SSNMR, also including the study of (1)H spin-lattice relaxation times. The research encompassed in vivo oral absorption studies in rats, pharmacokinetic analysis and physical stability studies during 1 year. An intimate drug-polymer mixing was found in the coground samples with domain average dimensions smaller than 100 Å; this reflected in a remarkable enhancement of the in vitro and in vivo bioavailability. Different disordered states were detected in the coground samples as a function of cogrinding time and the type and amount of polymer used. Though both crosslinked polymers produced a remarkable enhancement of the oral bioavailability, coground systems based on AcDiSol(®) are preferable in terms of pharmacokinetic performance and physical stability. PMID:22721852

  9. Organic field-effect transistors based on a crosslinkable polymer blend as the semiconducting layer

    NASA Astrophysics Data System (ADS)

    Yan, He; Yoon, Myung-Han; Facchetti, Antonio; Marks, Tobin J.

    2005-10-01

    For fabrication of top-gate polymer-based organic field-effect transistors (OFETs), it is essential that the semiconducting layer remain intact during spin coating of the overlying dielectric layer. This requirement severely limits the applicable solvent and materials combinations. We show here that a crosslinkable polymer blend consisting of a p-type semiconducting polymer {e.g., TFB; poly[9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine]} and an electroactive crosslinkable silyl reagent {e.g., TPDSi2; 4,4'-bis[(p-trichloro-silylpropylphenyl)phenylamino]biphenyl} is effective as the semiconducting layer in a top-gate bottom-contact OFET device. The TFB +TPDSi2 semiconducting blend is prepared by spin-coating in ambient. The crosslinking process occurs during spin-coating in air and is completed by curing at 90 °C, which renders the resulting film insoluble in common organic solvents and allows subsequent deposition of dielectric layers from a wide range of organic solvents. We also show that the presence of TPDSi2 in the semiconductor layer significantly reduces typical TFB-source-drain threshold voltages in bottom-contact devices, likely due to favorable interfacial TPDSi2-gold electrode interactions.

  10. Computational modeling of mechanical response of dual cross-linked polymer grafted nanoparticle networks

    NASA Astrophysics Data System (ADS)

    v S, Balaji; Yashin, Victor; Salib, Isaac; Kowalewski, Tomasz; Matyjaszewski, Krzystof; Balazs, Anna; Anna Balazs Collaboration; Krzystof Matyjaszewski Collaboration

    2013-03-01

    We develop a hybrid computational model for the behavior of a network of cross-linked polymer-grafted nanoparticles (PGNs). The individual nanoparticles are composed of a rigid core and a corona of grafted polymers that encompass reactive end groups. With the overlap of the coronas on adjacent particles, the reactive end groups can form permanent or labile bonds, which lead to the formation of a ``dual cross-linked'' network. To capture these multi-scale interactions, our approach integrates the essential structural features of the polymer grafted nanoparticles, the interactions between the overlapping coronas, and the kinetics of bond formation and rupture between the reactive groups on the chain ends. We investigate the mechanical response of the dual-cross linked network to an applied tensile deformation. We find that the response depends on the bond energies of the labile bonds, the fraction of permanent bonds in the network, and thickness of the corona. This model provides a powerful tool for the computational design of dual cross-linked PGN's by predicting how the structural features of the system affect the mechanical performance.

  11. Diffusion Coefficients of Water and Leachables in Methacrylate-based Crosslinked Polymers using Absorption Experiments

    PubMed Central

    Parthasarathy, Ranganathan; Misra, Anil; Park, Jonggu; Ye, Qiang; Spencer, Paulette

    2012-01-01

    The diffusion of water into dentin adhesive polymers and leaching of unpolymerized monomer from the adhesive are linked to their mechanical softening and hydrolytic degradation. Therefore, diffusion coefficient data are critical for the mechanical design of these polymeric adhesives. In this study, diffusion coefficients of water and leachables were obtained for sixteen methacrylate-based crosslinked polymers using absorption experiments. The experimental mass change data was interpreted using numerical solution of the two-dimensional diffusion equations. The calculated diffusion coefficients varied from 1.05 × 10−8 cm2/sec (co-monomer TMTMA) to 3.15 × 10−8 cm2/sec (co-monomer T4EGDMA). Correlation of the diffusion coefficients with crosslink density and hydrophilicity showed an inverse trend (R2 = 0.41). The correlation of diffusion coefficient with crosslink density and hydrophilicity are closer for molecules differing by simple repeat units (R2 = 0.95). These differences in the trends reveal mechanisms of interaction of the diffusing water with the polymer structure. PMID:22430592

  12. 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

  13. 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.

  14. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  15. Synthesis and characterization of cross-linkable polyurethane-imide electro-optic waveguide polymer

    NASA Astrophysics Data System (ADS)

    Wang, Long-De; Tang, Jie; Li, Ruo-Zhou; Zhang, Tong; Tong, Ling; Tang, Jing

    2016-01-01

    The novel electro-optic (EO) polymers of fluorinated cross-linkable polyurethane-imides (CLPUI) were designed and synthesized by polycondensation of azo chromophore C1 and C2, diisocyanate MDI, and aromatic dianhydride 6FDA. Molecular structural characterization for the resulting polymers was achieved by 1HNMR, FT-IR, elemental analysis, and gel permeation chromatography. The polymers exhibit good film-forming properties, high glass transition temperature ( T g) in the range of 193-200 °C, and thermal stability up to 290 °C. The polymers that possess a high EO coefficient (γ_{33} = 48 and 56 pm/V) at 1550 nm for poled polymer thin films were measured by the simple reflection technique. Excellent temporal stability and low optical losses in the range of 1.1-1.7 dB/cm at 1550 nm were observed for these polymers. Using the synthesized side-chain electro-optic CLPUI as the active core material and of a fluorinated polyimide as cladding material, we have designed and successfully fabricated the high-performance polymer waveguide Mach-Zehnder EO modulators.

  16. Size-exclusion partitioning of neutral solutes in crosslinked polymer networks: A Monte Carlo simulation study

    SciTech Connect

    Quesada-Pérez, Manuel; Maroto-Centeno, José Alberto; Adroher-Benítez, Irene

    2014-05-28

    In this work, the size-exclusion partitioning of neutral solutes in crosslinked polymer networks has been studied through Monte Carlo simulations. Two models that provide user-friendly expressions to predict the partition coefficient have been tested over a wide range of volume fractions: Ogston's model (especially devised for fibrous media) and the pore model. The effects of crosslinking and bond stiffness have also been analyzed. Our results suggest that the fiber model can acceptably account for size-exclusion effects in crosslinked gels. Its predictions are good for large solutes if the fiber diameter is assumed to be the effective monomer diameter. For solutes sizes comparable to the monomer dimensions, a smaller fiber diameter must be used. Regarding the pore model, the partition coefficient is poorly predicted when the pore diameter is estimated as the distance between adjacent crosslinker molecules. On the other hand, our results prove that the pore sizes obtained from the pore model by fitting partitioning data of swollen gels are overestimated.

  17. Citric acid-derived in situ crosslinkable biodegradable polymers for cell delivery

    PubMed Central

    Gyawali, Dipendra; Nair, Parvathi; Zhang, Yi; Tran, Richard T.; Zhang, Chi; Samchukov, Mikhail; Makarov, Marina; Kim, Harry; Yang, Jian

    2010-01-01

    Herein, we report the first citric acid (CA)-derived in situ crosslinkable biodegradable polymer, poly(ethylene glycol) maleate citrate (PEGMC). The synthesis of PEGMC could be carried out via a one-pot polycondensation reaction without using organic solvents or catalysts. PEGMC could be in-situ crosslinked into elastomeric PPEGMC hydrogels. The performance of hydrogels in terms of swelling, degradation, and mechanical properties were highly dependent on the molar ratio of monomers, crosslinker concentration, and crosslinking mechanism used in the synthesis process. Cyclic conditioning tests showed that PPEGMC hydrogels could be compressed up to 75% strain without permanent deformation and with negligible hysteresis. Water-soluble PEGMC demonstrated excellent cytocompatibilty in vitro. The degradation products of PPEGMC also showed minimal cytotoxicity in vitro. Animal studies in rats clearly demonstrated the excellent injectability of PEGMC and degradability of the in situ-formed PPEGMC. PPEGMC elicited minimal inflammation in the early stages post-injection and was completely degraded within 30 days in rats. In conclusion, the development of CA-derived injectable biodegradable PEGMC presents numerous opportunities for material innovation and offers excellent candidate materials for in situ tissue engineering and drug delivery applications. PMID:20800893

  18. Magnetically Controllable Polymer Nanotubes from a Cyclized Crosslinker for Site-Specific Delivery of Doxorubicin.

    PubMed

    Newland, Ben; Leupelt, Daniel; Zheng, Yu; Thomas, Laurent S V; Werner, Carsten; Steinhart, Martin; Wang, Wenxin

    2015-01-01

    Externally controlled site specific drug delivery could potentially provide a means of reducing drug related side effects whilst maintaining, or perhaps increasing therapeutic efficiency. The aim of this work was to develop a nanoscale drug carrier, which could be loaded with an anti-cancer drug and be directed by an external magnetic field. Using a single, commercially available monomer and a simple one-pot reaction process, a polymer was synthesized and crosslinked within the pores of an anodized aluminum oxide template. These polymer nanotubes (PNT) could be functionalized with iron oxide nanoparticles for magnetic manipulation, without affecting the large internal pore, or inherent low toxicity. Using an external magnetic field the nanotubes could be regionally concentrated, leaving areas devoid of nanotubes. Lastly, doxorubicin could be loaded to the PNTs, causing increased toxicity towards neuroblastoma cells, rendering a platform technology now ready for adaptation with different nanoparticles, degradable pre-polymers, and various therapeutics. PMID:26619814

  19. Magnetically Controllable Polymer Nanotubes from a Cyclized Crosslinker for Site-Specific Delivery of Doxorubicin

    NASA Astrophysics Data System (ADS)

    Newland, Ben; Leupelt, Daniel; Zheng, Yu; Thomas, Laurent S. V.; Werner, Carsten; Steinhart, Martin; Wang, Wenxin

    2015-12-01

    Externally controlled site specific drug delivery could potentially provide a means of reducing drug related side effects whilst maintaining, or perhaps increasing therapeutic efficiency. The aim of this work was to develop a nanoscale drug carrier, which could be loaded with an anti-cancer drug and be directed by an external magnetic field. Using a single, commercially available monomer and a simple one-pot reaction process, a polymer was synthesized and crosslinked within the pores of an anodized aluminum oxide template. These polymer nanotubes (PNT) could be functionalized with iron oxide nanoparticles for magnetic manipulation, without affecting the large internal pore, or inherent low toxicity. Using an external magnetic field the nanotubes could be regionally concentrated, leaving areas devoid of nanotubes. Lastly, doxorubicin could be loaded to the PNTs, causing increased toxicity towards neuroblastoma cells, rendering a platform technology now ready for adaptation with different nanoparticles, degradable pre-polymers, and various therapeutics.

  20. Microstructured Films Formed on Liquid Substrates via Initiated Chemical Vapor Deposition of Cross-Linked Polymers.

    PubMed

    Bradley, Laura C; Gupta, Malancha

    2015-07-28

    We studied the formation of microstructured films at liquid surfaces via vapor phase polymerization of cross-linked polymers. The films were composed of micron-sized coral-like structures that originate at the liquid-vapor interface and extend vertically. The growth mechanism of the microstructures was determined to be simultaneous aggregation of the polymer on the liquid surface and wetting of the liquid on the growing aggregates. We demonstrated that we can increase the height of the microstructures and increase the surface roughness of the films by either decreasing the liquid viscosity or decreasing the polymer deposition rate. Our vapor phase method can be extended to synthesize functional, free-standing copolymer microstructured thin films for potential applications in tissue engineering, electrolyte membranes, and separations. PMID:26176742

  1. Magnetically Controllable Polymer Nanotubes from a Cyclized Crosslinker for Site-Specific Delivery of Doxorubicin

    PubMed Central

    Newland, Ben; Leupelt, Daniel; Zheng, Yu; Thomas, Laurent S. V.; Werner, Carsten; Steinhart, Martin; Wang, Wenxin

    2015-01-01

    Externally controlled site specific drug delivery could potentially provide a means of reducing drug related side effects whilst maintaining, or perhaps increasing therapeutic efficiency. The aim of this work was to develop a nanoscale drug carrier, which could be loaded with an anti-cancer drug and be directed by an external magnetic field. Using a single, commercially available monomer and a simple one-pot reaction process, a polymer was synthesized and crosslinked within the pores of an anodized aluminum oxide template. These polymer nanotubes (PNT) could be functionalized with iron oxide nanoparticles for magnetic manipulation, without affecting the large internal pore, or inherent low toxicity. Using an external magnetic field the nanotubes could be regionally concentrated, leaving areas devoid of nanotubes. Lastly, doxorubicin could be loaded to the PNTs, causing increased toxicity towards neuroblastoma cells, rendering a platform technology now ready for adaptation with different nanoparticles, degradable pre-polymers, and various therapeutics. PMID:26619814

  2. Analyses of viscoelastic solid polymers undergoing degradation

    NASA Astrophysics Data System (ADS)

    Davoodi, Bentolhoda; Muliana, Anastasia; Tscharnuter, Daniel; Pinter, Gerald

    2015-08-01

    In this paper we study the three-dimensional response of isotropic viscoelastic solid-like polymers undergoing degradation due to mechanical stimuli. A single integral model is used to describe the time-dependent behaviors of polymers under general loading histories. The degradation is associated to excessive deformations in the polymers as strains continuously increase when the mechanical stimuli are prescribed, and therefore we consider a degradation threshold in terms of strains. The degradation part of the deformations is unrecoverable, and upon removal of the prescribed external stimuli, the accumulation of the degradation strains lead to residual strains. We also systematically present material parameter characterization from available experimental data under various loading histories, i.e., ramp loading with different constant rates, creep-recovery under different stresses, and relaxation under several strains. We analyze viscoelastic-degradation response of two polymers, namely polyethylene and polyoxymethylene under uniaxial tensile tests. Longer duration of loading can lead to increase in the degradation of materials due to the substantial increase in the deformations. The single integral model is capable in predicting the time-dependent responses of the polymers under various loading histories and capturing the recovery and residual strains at different stages of degradations.

  3. Improved lithium-metal/vanadium pentoxide polymer battery incorporating crosslinked ternary polymer electrolyte with N-butyl-N-methylpyrrolidinium bis(perfluoromethanesulfonyl)imide

    NASA Astrophysics Data System (ADS)

    Osada, Irene; von Zamory, Jan; Paillard, Elie; Passerini, Stefano

    2014-12-01

    Li metal polymer batteries incorporating crosslinked ternary PEO/PYR14TFSI/LiTFSI solid polymer electrolyte (SPE) have been prepared, using V2O5 as active cathode material. As a result of the optimization of the SPE as well as the cell assembly and cycling conditions, V2O5 lithium metal polymer batteries allow reaching 796 Wh kg-1 (of V2O5) at C/10 at 40 °C and maintaining 663 Wh kg-1 after 200 cycles at 40 °C. This is higher than the theoretical specific energy of LiCoO2 vs. Li of 609 Wh kg-1. Cycling at 80 °C allows reaching 270 mAh g-1 at C/2 and 210 mAh g-1 at 1 C, while at 20 °C it is still possible to reach a discharge capacity of almost 100 mAh g-1 at low rates. Post-cycling SEM and EDX imaging showed that, after 200 cycles at 40 °C, if the plating of Li is not fully homogeneous, no sign of dendrite growth nor obvious vanadium dissolution and redeposition on the anode side occurred.

  4. Solid polymer MEMS-based fuel cells

    DOEpatents

    Jankowski, Alan F.; Morse, Jeffrey D.

    2008-04-22

    A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

  5. Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Shim, Jimin; Bae, Ki Yoon; Kim, Hee Joong; Lee, Jin Hong; Kim, Dong-Gyun; Yoon, Woo Young; Lee, Jong-Chan

    2015-12-21

    Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4)  Scm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1 wt %) of the crosslinking agent and 2.0 wt % of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state. PMID:26609912

  6. A Synthetic Fibrin-Crosslinking Polymer for Modulating Clot Properties and Inducing Hemostasis

    PubMed Central

    Chan, Leslie W.-G.; Wang, Xu; Wei, Hua; Pozzo, Lilo D.; White, Nathan J.; Pun, Suzie H.

    2015-01-01

    Clotting factor replacement is the standard management of acute bleeding in congenital and acquired bleeding disorders. We present a synthetic approach to hemostasis using an engineered hemostatic polymer (PolySTAT) that circulates innocuously in the blood, identifies sites of vascular injury, and promotes clot formation to stop bleeding. PolySTAT induces hemostasis by crosslinking the fibrin matrix within clots, mimicking the function of the transglutaminase Factor XIII. Furthermore, synthetic PolySTAT binds specifically to fibrin monomers and is uniformly integrated into fibrin fibers during fibrin polymerization, resulting in a fortified, hybrid polymer network with enhanced resistance to enzymatic degradation. In vivo hemostatic activity was confirmed in a rat model of trauma and fluid resuscitation in which intravenous administration of PolySTAT improved survival by reducing blood loss and resuscitation fluid requirements. PolySTAT-induced fibrin crosslinking is a novel approach to hemostasis utilizing synthetic polymers for non-invasive modulation of clot architecture with potentially wide-ranging therapeutic applications. PMID:25739763

  7. 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

  8. Synthesis and optical properties of a crosslinkable polymer system containing TCF and TCP chromophores with excellent electro-optic activity and thermal stability

    NASA Astrophysics Data System (ADS)

    Chen, Zhuo; Bo, Shuhui; Zhen, Zhen; Liu, Xinhou

    2012-10-01

    Crosslinkable polymer with side-chain system was investigated to increase the content of NLO chromophores and improve the stability of oriented chromophores. In this work, a series of crosslinkable copolymers which beared different concentrations of chromophores with the tricyanofurane (TCF) acceptor and a kind of crosslinkable copolymers beared chromophores with dendritic tricyanopyrroline (TCP) acceptor were successfully synthesized and characterized. The crosslinked EO polymers which beared chromophores with the tricyanofurane (TCF) acceptor revealed the highest EO coefficient (r33) of 47.0 pm/V at 1310 nm, which was similar with the r33 of uncrosslinked systems. Compared to the uncrosslinked EO polymer systems, the crosslinked ones exhibited significantly enhanced temporal stability. Keywords: Nonlinear optics; Crosslinkable system; Chromophore-containing copolymers; Side-chain; Crosslinking reaction; Thermally stable polymer

  9. Solid polymer electrolyte from phosphorylated chitosan

    SciTech Connect

    Fauzi, Iqbal Arcana, I Made

    2014-03-24

    Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

  10. Synthesis of chitosan molecularly imprinted polymers for solid-phase extraction of methandrostenolone.

    PubMed

    Wang, Yun; Wang, Enlan; Wu, Ziming; Li, Huan; Zhu, Zhi; Zhu, Xinsheng; Dong, Ying

    2014-01-30

    Chitosan molecularly imprinted polymers (CHI-MIPs) for selective extraction of methandrostenolone (MA) was synthesized by cross-linking of chitosan with epichlorohydrin in the presence of MA as the template molecule. Systematic investigations of the influences of template, functional polymer, cross-linker as well as porogen concentrations on the rebinding capacity of CHI-MIPs were carried out. Adsorption and kinetic binding experiments indicated that the synthesized CHI-MIPs had high adsorption and excellent affinity to MA. Solid-phase extraction (SPE) using the prepared CHI-MIPs as adsorbent was then investigated, and the optimum loading and eluting conditions for SPE of the MA were established. The optimized SPE procedure was used to extract the MA from several spiked samples and a good sample clean-up was obtained with the average recoveries ranged from 95.97 to 101.79%. PMID:24299807

  11. Integrated reactive ion etching to pattern cross-linked hydrophilic polymer structures for protein immobilization

    NASA Astrophysics Data System (ADS)

    Bhatnagar, Parijat; Strickland, Aaron D.; Kim, Il; Malliaras, George G.; Batt, Carl A.

    2007-04-01

    Patterning of cross-linked hydrophilic polymer features using reactive ion etching (RIE) capable of covalently immobilizing proteins has been achieved. Projection photolithography was used to pattern photoresist to create micromolds. Vapor phase molecular self-assembly of polymerizable monolayer in molds allowed covalent binding of hydrogel on surface during free-radical polymerization. Excess hydrogel blanket film was consumed with oxygen RIE resulting into hydrogel pattern of 1μm size aligned to prefabricated silicon oxide structures. Proteins were finally coupled through their primary amine groups selectively to acid functionalized hydrogel features through stable amide linkages using 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride and N-hydroxysulfosuccinimide.

  12. Ionic liquids-based crosslinked copolymer sorbents for headspace solid-phase microextraction of polar alcohols.

    PubMed

    Feng, Juanjuan; Sun, Min; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang

    2012-07-01

    Halogen-based polymeric ionic liquid (PIL) fibers, which have proved efficient for solid-phase microextraction (SPME) of polar compounds, were with very limited fiber lifetimes. In this work, a novel crosslinked PIL sorbent with satisfactory stability and durability was prepared in situ via crosslinking polymerization processes on microstructured-silver coated stainless steel wire. 1,1'-(1,6-Hexanediyl)bis(1-vinylimidazolium) bibromide ionic liquid was synthesized and used as the crosslinking agent, with 1-vinyl-3-octylimidazolium bromide as monomer. Extraction properties of the fiber for polar alcohols in polar aqueous matrix were examined using headspace SPME (HS-SPME) coupled to gas chromatography-flame ionization detection (GC-FID). Under the optimized extraction and desorption conditions, the established method exhibited high extraction capacity. Wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9947 to 0.9999. Limits of detection were in the range of 0.5-20 μg L⁻¹. Compared with the non-crosslinked PIL fiber, the proposed crosslinked PIL fiber was with higher thermal stability and durability and longer lifetime. Four different liquor beverages were analyzed as real samples and good results were obtained. PMID:22673810

  13. 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.

  14. Diffusivity and Transient Localization of Filler Particles in Polymer Melts and Crosslinked Systems

    NASA Astrophysics Data System (ADS)

    Dell, Zachary E.; Schweizer, Kenneth S.

    2013-03-01

    Building on recent progress in describing the microscopic equilibrium structure of polymer nanocomposites (PRISM theory), as well as the naïve mode coupling and nonlinear Langevin equation approaches for predicting localization and activated barrier hopping, we have initiated the study of dynamical phenomena in nanocomposites at finite filler loading. A colloidal suspension perspective is adopted whereby the polymer dynamics are assumed to remain unperturbed by fillers. Both entangled polymer melts and crosslinked systems are studied. The long time behavior of a tagged nanoparticle (localization and diffusivity) is calculated for various melt (tube diameter, polymer radius of gyration) and nanoparticle (filler size and volume fraction, polymer-filler attraction strength) parameters. For transiently localized particles, a dynamic free energy is constructed and employed to compute the nanoparticle localization length, mean barrier hopping time, and self-diffusion constant. The influence of filler-filler interactions on the Stokes-Einstein violation phenomenon in entangled melts is established. In addition, the influence of nanocomposite statistical structure (e.g., in the depletion, steric stabilization, or bridging regimes) on slow dynamics and localization is investigated.

  15. Rheology of cross-linked polymers and polymer foams: Theory and experimental results

    NASA Astrophysics Data System (ADS)

    Herman, John N.

    Typical polymers have a time-dependent response to loading which results in stress relaxation or creep. Models using springs/dashpots or Volterra integrals are capable of predicting the material response, but place little or no emphasis on the reasoning behind the response. This research proposes a microscopic reasoning behind polymer chain movement, while developing a model to predict the creep and stress relaxation of a polymer foam. Based on the theorized slip/stick of polymer chains as they slide past each other, this model successfully predicts the behavior of a PMI polymer foam under tensile loads. This model lends insights into polymer microscopic behavior, which may be used for the development of future polymer materials. When possible, industry standard test methods are used to obtain tensile creep and stress relaxation results from rectangular specimens of Rohacell 31 IG foam. A common set of material parameters is fitted to the data, validating the micromechanic reasoning to polymer chain movement. To gain insight into observed test result variability, an investigation of the elastic modulus and material density relationship is performed using nominal foam densities of 31 kg/m3, 51 kg/m3,, 71 kg/m3. Additional testing and modeling is performed to validate the model under load/partial-unload/ hold, load/unload/recovery, and load/instantaneous-unload test cycles. The model successfully captures the observed material nuances during these more complex loading cycles.

  16. Fabrication of Hollow Microporous Carbon Spheres from Hyper-Crosslinked Microporous Polymers.

    PubMed

    Wang, Kewei; Huang, Liang; Razzaque, Shumaila; Jin, Shangbin; Tan, Bien

    2016-06-01

    Porous carbon materials prepared from the porous organic polymers are currently the subject of extensive investigation. On the basis of their interesting applications, it is highly desirable to develop new synthetic methodologies to obtain carbon materials with controllable pore size and morphology. Herein, a facile synthesis of hollow microporous carbon spheres (HCSs) from hollow microporous organic capsules (HMOCs) with a good control over the pore morphology, hollow cavity, and the shell thickness is reported. The highly porous hollow carbon spheres are prepared by the pyrolysis of HMOCs-based microporous polymers. The synthetic parameters, such as hypercrosslinking and pyrolysis conditions, are optimized to modify the porous structures and the properties. The morphology and porosity as well as energy storage applications of the microporous structures HCSs, derived through a combination of divinylbenzene-crosslinking and micropore-generating hypercrosslinking, are discussed. These findings provide a new benchmark for fabricating well-defined HCSs with great promise for various applications. PMID:27145206

  17. Long-term biostability of self-assembling protein polymers in the absence of covalent crosslinking.

    PubMed

    Sallach, Rory E; Cui, Wanxing; Balderrama, Fanor; Martinez, Adam W; Wen, Jing; Haller, Carolyn A; Taylor, Jeannette V; Wright, Elizabeth R; Long, Robert C; Chaikof, Elliot L

    2010-02-01

    Unless chemically crosslinked, matrix proteins, such as collagen or silk, display a limited lifetime in vivo with significant degradation observed over a period of weeks. Likewise, amphiphilic peptides, lipopeptides, or glycolipids that self-assemble through hydrophobic interactions to form thin films, fiber networks, or vesicles do not demonstrate in vivo biostability beyond a few days. We report herein that a self-assembling, recombinant elastin-mimetic triblock copolymer elicited minimal inflammatory response and displayed robust in vivo stability for periods exceeding 1 year, in the absence of either chemical or ionic crosslinking. Specifically, neither a significant inflammatory response nor calcification was observed upon implantation of test materials into the peritoneal cavity or subcutaneous space of a mouse model. Moreover, serial quantitative magnetic resonance imaging, evaluation of pre- and post-explant ultrastructure by cryo-high resolution scanning electron microscopy, and an examination of implant mechanical responses revealed substantial preservation of form, material architecture, and biomechanical properties, providing convincing evidence of a non-chemically or ionically crosslinked protein polymer system that exhibits long-term stability in vivo. PMID:19854505

  18. H2O2-treated actin: assembly and polymer interactions with cross-linking proteins.

    PubMed Central

    DalleDonne, I; Milzani, A; Colombo, R

    1995-01-01

    During inflammation, hydrogen peroxide, produced by polymorphonuclear leukocytes, provokes cell death mainly by disarranging filamentous (polymerized) actin (F-actin). To show the molecular mechanism(s) by which hydrogen peroxide could alter actin dynamics, we analyzed the ability of H2O2-treated actin samples to polymerize as well as the suitability of actin polymers (from oxidized monomers) to interact with cross-linking proteins. H2O2-treated monomeric (globular) actin (G-actin) shows an altered time course of polymerization. The increase in the lag phase and the lowering in both the polymerization rate and the polymerization extent have been evidenced. Furthermore, steady-state actin polymers, from oxidized monomers, are more fragmented than control polymers. This seems to be ascribable to the enhanced fragility of oxidized filaments rather than to the increase in the nucleation activity, which markedly falls. These facts; along with the unsuitability of actin polymers from oxidized monomers to interact with both filamin and alpha-actinin, suggest that hydrogen peroxide influences actin dynamics mainly by changing the F-actin structure. H2O2, via the oxidation of actin thiols (in particular, the sulfhydryl group of Cys-374), likely alters the actin C-terminus, influencing both subunit/subunit interactions and the spatial structure of the binding sites for cross-linking proteins in F-actin. We suggest that most of the effects of hydrogen peroxide on actin could be explained in the light of the "structural connectivity," demonstrated previously in actin. Images FIGURE 3 FIGURE 9 PMID:8599677

  19. Solid-Phase Cross-Linking (SPCL): a new tool for protein structure studies.

    PubMed

    Paramelle, David; Enjalbal, Christine; Amblard, Muriel; Forest, Eric; Heymann, Michaël; Cantel, Sonia; Geourjon, Christophe; Martinez, Jean; Subra, Gilles

    2011-04-01

    A wide range of chemical reagents are available to study the protein-protein interactions or protein structures. After reaction with such chemicals, covalently modified proteins are digested, resulting in shorter peptides that are analyzed by mass spectrometry (MS). Used especially when NMR of X-ray data are lacking, this methodology requires the identification of modified species carrying relevant information, among the unmodified peptides. To overcome the drawbacks of existing methods, we propose a more direct strategy relying on the synthesis of solid-supported cleavable monofunctional reagents and cross-linkers that react with proteins and that selectively release, after protein digestion and washings, the modified peptide fragments ready for MS analysis. Using this Solid-Phase Cross-Linking (SPCL) strategy, only modified sequences are analyzed and consistent data can be easily obtained since the signals of interest are not masked or suppressed by over-represented unmodified materials. PMID:21319301

  20. Strain recovery in dual cross-linked polymer grafted nanoparticle networks

    NASA Astrophysics Data System (ADS)

    v S, Balaji; Yashin, Victor; Salib, Isaac; Kowalewski, Tomasz; Matyjaszewski, Krzystof; Balazs, Anna; Anna Balazs Collaboration; Krzystof Matyjaszewski Collaboration

    2013-03-01

    Via computational modeling, we investigate the mechanism of strain-recovery in dual cross-linked polymer grafted nanoparticle networks. The individual nanoparticles are composed of a rigid core and a corona of grafted polymers that encompass reactive end groups. With the overlap of the coronas on adjacent particles, the reactive end groups form permanent or labile bonds, and thus form a ``dual cross-linked'' network. We consider the strain recovery of the material after it is allowed to relax from the application of the tensile force. We apply multiple cycles of tension and relaxation and determine how the stress-strain curves change in the course of these repetitive deformations. Notably, the existing labile bonds can break and new bonds can form in the course of deformation. Hence, a damaged material could be ``rejuvenated'' both in terms of the recovery of strain and the number of bonds, if the relaxation occurs over a sufficiently long time. We show that this rejuvenation depends on the fraction of permanent bonds, strength of labile bonds, and maximal strain.

  1. Molecular-level modeling of the viscoelasticity of crosslinked polymers: Effect of time and temperature

    SciTech Connect

    Simon, P.P.; Ploehn, H.J.

    1997-05-01

    We present a new molecular-level picture of chain dynamics for describing the viscoelasticity of crosslinked polymers. The associated mathematical model consists of a time-dependent momentum balance on a representative polymer segment in the crosslinked network, plus phenomenological expressions for forces acting on the segments. These include a cohesive force that accounts for intermolecular attraction, an entropic force describing the thermodynamics governing chain conformations, and a frictional force that captures the temperature dependence of relative chain motion. We treat the case of oscillatory uniaxial deformation. Solution of the model equations in the frequency domain yields the dynamic moduli as functions of temperature and frequency. The model reproduces all of the qualitative features of experimental dynamic modulus data across the complete spectrum of time and temperature, spanning the glassy zone, the {beta} transition, the dynamic glass transition, and the rubbery zone. All of the model parameters can be evaluated through the use of independent experimental data. Comparison of model predictions with experimental data yields good quantitative agreement outside of the glass transition region. {copyright} {ital 1997 Society of Rheology.}

  2. 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.

  3. New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

    NASA Technical Reports Server (NTRS)

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

    2005-01-01

    A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

  4. Ionic polymer metal composite actuators employing irradiation-crosslinked sulfonated poly(styrene-ran-ethylene) as ion-exchange membranes

    NASA Astrophysics Data System (ADS)

    Wang, Xuanlun; Cheng, Tai-Hong; Xu, Liang; Oh, Il-Kwon

    2009-07-01

    Ionic polymer metal composites (IPMC) are soft polymeric smart materials having large displacement at low voltage in moist environments or water. This type of actuators consists of an ionic membrane and noble metal electrodes plated on both surfaces. The ion-exchange membrane, Nafion, remains as the benchmark for a majority of research and development in IPMC technology. In this research, we employed sulfonated poly(styrene-ran-ethylene) (SPSE) that is crosslinked by UV irradiation as a novel ionic membrane. The crosslinking reaction between polymer matrix and crosslinking agent was proved by FTIR analysis. The sulfonic acid groups were stable during the UV irradiation crosslinking process. Water uptake, ion exchange capacity, and sulfonation degree are characterized for both pure SPSE and crosslinked SPSE membrane. The bending responses of SPSE actuators under both direct current (DC) and alternating current (AC) excitations were investigated. The voltage-current behaviors of the actuators under AC excitations are also measured. Results showed the crosslinked SPSE actuators have better electromechanical performance than that of pure SPSE actuator with regard to tip displacement.

  5. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

    PubMed Central

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-01-01

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246

  6. Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

    NASA Technical Reports Server (NTRS)

    Leventis, Nicholas

    2005-01-01

    In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect

  7. Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries.

    PubMed

    Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G; Lee, Yoon-Sung; Kim, Dong-Won

    2016-01-01

    Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

  8. Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

    NASA Astrophysics Data System (ADS)

    Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

    2016-05-01

    Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures.

  9. Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

    PubMed Central

    Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

    2016-01-01

    Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

  10. Radiation-crosslinking of shape memory polymers based on poly(vinyl alcohol) in the presence of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Basfar, A. A.; Lotfy, S.

    2015-01-01

    Shape memory polymers based on poly(vinyl alcohol) (SM-PVA) in the presence of 2-carboxyethyl acrylate oligomers (CEA) and multi-wall carbon nanotubes (MWCNTs) crosslinked by ionizing radiation were investigated. Chemical-crosslinking of PVA by glutaraldehyde in the presence of CEA and MWCNTs was also studied. The swelling and gel fraction of the radiation-crosslinked SM-PVA and chemically crosslinked systems were evaluated. Analysis of the swelling and gel fraction revealed a significant reduction in swelling and an increase in the gel fraction of the material that was chemically crosslinked with glutaraldehyde. The radiation-crosslinked SM-PVA demonstrated 100% gelation at an irradiation dose of 50 kGy. In addition, radiation-crosslinked SM-PVA exhibited good temperature responsive shape-memory behavior. A scanning electron microscopy (SEM) analysis was performed. The thermal properties of radiation-crosslinked SM-PVA were investigated by a thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The ability of the material to return or store energy (E‧), to its ability to lose energy (E″), and the ratio of these effects (Tanδ), which is called damping were examined via DMA. The temperature of Tanδ in the radiation-crosslinked SM-PVA decreased significantly by 6 and 13 °C as a result of the addition of MWCNTs. In addition, the temperature of Tanδ for SM-PVA increased as the irradiation dose increased. These radiation-crosslinked SM-PVA materials show promising shape-memory behavior based on the range of temperatures at which Tanδ appears.

  11. Solid Polymer Electrolyte Fuel Cell Technology Program

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Work is reported on phase 5 of the Solid Polymer Electrolyte (SPE) Fuel Cell Technology Development program. The SPE fuel cell life and performance was established at temperatures, pressures, and current densities significantly higher than those previously demonstrated in sub-scale hardware. Operation of single-cell Buildup No. 1 to establish life capabilities of the full-scale hardware was continued. A multi-cell full-scale unit (Buildup No. 2) was designed, fabricated, and test evaluated laying the groundwork for the construction of a reactor stack. A reactor stack was then designed, fabricated, and successfully test-evaluated to demonstrate the readiness of SPE fuel cell technology for future space applications.

  12. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  13. Solid particle erosion of polymers and composites

    NASA Astrophysics Data System (ADS)

    Friedrich, K.; Almajid, A. A.

    2014-05-01

    After a general introduction to the subject of solid particle erosion of polymers and composites, the presentation focusses more specifically on the behavior of unidirectional carbon fiber (CF) reinforced polyetheretherketone (PEEK) composites under such loadings, using different impact conditions and erodents. The data were analyzed on the basis of a newly defined specific erosive wear rate, allowing a better comparison of erosion data achieved under various testing conditions. Characteristic wear mechanisms of the CF/PEEK composites consisted of fiber fracture, matrix cutting and plastic matrix deformation, the relative contribution of which depended on the impingement angles and the CF orientation. The highest wear rates were measured for impingement angles between 45 and 60°. Using abrasion resistant neat polymer films (in this case PEEK or thermoplastic polyurethane (TPU) ones) on the surface of a harder substrate (e.g. a CF/PEEK composite plate) resulted in much lower specific erosive wear rates. The use of such polymeric films can be considered as a possible method to protect composite surfaces from damage caused by minor impacts and erosion. In fact, they are nowadays already successfully applied as protections for wind energy rotor blades.

  14. Near-ambient solid polymer fuel cell

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.

    1993-01-01

    Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as

  15. Fluorescent cross-linked supramolecular polymers constructed from a novel self-complementary AABB-type heteromultitopic monomer.

    PubMed

    Fang, Le; Hu, Yuanli; Li, Qiang; Xu, Shutao; Dhinakarank, Manivannan Kalavathi; Gong, Weitao; Ning, Guiling

    2016-04-26

    A novel AABB-type heteromultitopic monomer (), having a self-complementary perpendicular structure, could solely self-assemble to fluorescent cross-linked supramolecular polymers. Interestingly, the supramolecular gel film shows a sensitive fluorescence change on exposure to acid and base vapor, endowing this system with a potential application in gas detection. PMID:27005489

  16. Novel biobased photo-crosslinked polymer networks prepared from vegetable oil and 2,5-furan diacrylate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5-furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybe...

  17. The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers

    PubMed Central

    Hearon, Keith; Smith, Sarah E.; Maher, Cameron A.; Wilson, Thomas S.; Maitland, Duncan J.

    2012-01-01

    The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities—that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal

  18. Construction of monomer-free, highly crosslinked, water-compatible polymers.

    PubMed

    Dailing, E A; Lewis, S H; Barros, M D; Stansbury, J W

    2014-12-01

    Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. PMID:25248612

  19. Construction of Monomer-free, Highly Crosslinked, Water-compatible Polymers

    PubMed Central

    Dailing, E.A.; Lewis, S.H.; Barros, M.D.; Stansbury, J.W.

    2014-01-01

    Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. PMID:25248612

  20. Polymer coating of porcine decellularized and cross-linked aortic grafts.

    PubMed

    Heidenhain, Christoph; Weichert, Wilko; Schmidmaier, Gerhard; Wildemann, Britt; Hein, Moritz; Neuhaus, Peter; Heise, Michael

    2010-07-01

    This article investigates a method of modifying and optimizing the biocompatibility of decellularized vascular bioimplants when treated with a specialized, drug eluting coating. For this purpose, we carried out aortic transplantations using a porcine model. Decellularized, cross-linked aortic grafts were coated with poly(D,L-lactide) (PDLLA). To this coating, we added the anticoagulant drug lepirudin which, following transplantation, would be linearly eluted. These aortic grafts are easily manipulated in surgery. It was shown that, as a result of the lepirudin-eluting coating, the rate of thrombogenesis was reduced and the patency rate was significantly improved. However, lumen-stenosing pseudointima developed in all of the transplants and was not effected by PDLLA coating. Furthermore, no evidence of recellularisation was documented. This trial demonstrates that polymer coating of decellularized tissue is possible. Neointimal hyperplasia and the absence of cellular repopulation mark the negative consequences of this concept. PMID:20524202

  1. Photomobile polymer materials with crosslinked liquid-crystalline structures: molecular design, fabrication, and functions.

    PubMed

    Ube, Toru; Ikeda, Tomiki

    2014-09-22

    Crosslinked liquid-crystalline polymer materials that macroscopically deform when irradiated with light have been extensively studied in the past decade because of their potential in various applications, such as microactuators and microfluidic devices. The basic motions of these materials are contraction-expansion and bending-unbending, which are observed mainly in polysiloxanes and polyacrylates that contain photochromic moieties. Other sophisticated motions such as twisting, oscillation, rotation, and translational motion have also been achieved. In recent years, efforts have been made to improve the photoresponsive and mechanical properties of this novel class of materials through the modification of molecular structures, development of new fabrication methods, and construction of composite structures. Herein, we review structures, functions, and working mechanisms of photomobile materials and recent advances in this field. PMID:25196371

  2. Functional crosslinked polymer particles synthesized by precipitation polymerization for liquid chromatography.

    PubMed

    Perrier-Cornet, R; Héroguez, V; Thienpont, A; Babot, O; Toupance, T

    2008-01-25

    Highly crosslinked functional polymer particles with narrow size distribution have been produced by precipitation copolymerization of divinylbenzene, ethylene glycol dimethacrylate and vinylbenzyl chloride using a simple reflux protocol. After establishing the satisfactory synthesis conditions, we produced uniform chlorobenzyl particles with different size depending on the polymerization times. The porosity of those particles was modulated from microporous to mesoporous structure by using various porogens such as toluene, dodecanol, cyclohexanol and polypropylene glycol. These particles were tested as stationary phase in high-performance liquid chromatography for the separation of polycyclic aromatic hydrocarbons in reversed-phase mode. The separation was observed even for elution 100% organic (methanol) without any participation of water fraction in the eluent composition. The influences of particles size, specific surface area and packing conditions on the separation behavior were investigated. PMID:17936766

  3. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, T.A.

    1984-10-19

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  4. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, Terje A.

    1985-01-01

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  5. Ionically Crosslinked Polymer Networks for Underwater Adhesion and Long-Term Controlled Release

    NASA Astrophysics Data System (ADS)

    Lawrence, Patrick G.

    Underwater adhesives have several potential applications in industry as well as in medicine. Much of the recent research in this area has focused on adhesive preparation from biological or custom-designed biomimetic polymers. As a simpler alternative, we have recently shown that ionically crosslinked, gel-like underwater adhesive complexes can be prepared by the mixing of the readily-available and inexpensive polyelectrolyte, poly(allylamine hydrochloride) (PAH), with commonly-used multivalent anions, pyrophosphate (PPi) and tripolyphosphate (TPP). Remarkably, these gel-like complexes adhere to both hydrophilic and hydrophobic substrates under water with tensile adhesive strength considerably greater than that of Scotch Permanent Double Sided Tape (up to ˜400 kPa vs. ˜85 kPa when used as a pressure-sensitive adhesives) and due to the reversible nature of the ionic crosslinks, self-heal when torn. These complexes also exhibit very high storage moduli (greater than 100 kPa), indicative of a very high crosslink density. The high crosslink density allow these gel-like complexes to also entrap and deliver small molecule payloads over multiple-month timescales. Moreover, their formation and rheological/adhesion properties can be controlled using external stimuli (pH and ionic strength). In this thesis we characterize formation and rheological/adhesion properties of gel-like PAH/PPi and PAH/TPP complexes the through the use of dynamic and electrophoretic light scattering, rheology and tensile adhesion tests. We also describe their sensitivity to pH and ionic strength, and explain how the complexes can be dissolved on demand by raising or lowering the ambient pH, and can form spontaneously by increasing the NaCl concentration (which can be used for developing injectable underwater adhesive formulations). Finally, we demonstrate the ability of these adhesives to release small molecule payloads over multiple-month timescales by characterizing their ability to take up and

  6. Adsorption properties of cross-linked cellulose-epichlorohydrin polymers in aqueous solution.

    PubMed

    Udoetok, Inimfon A; Dimmick, Raquel M; Wilson, Lee D; Headley, John V

    2016-01-20

    Cellulose was cross-linked with epichlorohydrin (EP) at variable levels (CLE-0.5, CLE-2 and CLE-4), where CLE-i denotes the cellulose to EP mole ratios. The cross-linked products were characterized by TGA and FT-IR spectroscopy, pH at the point of zero charge (pHpzc), water swelling, and dye-adsorption methods employing two types of dyes [phenolphthalein (phth) and p-nitrophenol (PNP)]. The characterization methods provide evidence of cross-linking of cellulose in accordance with variations in surface area, PZC, available surface hydroxyl groups, and thermal stability when compared against pristine cellulose. The pHpzc of the sorbent materials was ∼ 6.5 indicating a negative surface charge occurs above pHpzc. The cross-linked polymers possess greater swelling properties relative to pristine cellulose. Detailed adsorption studies were carried out at pH 9 for cellulose and CLE-i with five types single component carboxylate anions [2-hexyldecanoic acid (S1), trans-4-pentylcyclohexanecarboxylic acid (S2), 2-dicyclohexylacetic acid (S3), adamantane carboxylic acid (S4), and cyclohexane carboxylic acid (S5)] at 295 K. The uptake properties of PNP with cellulose and CLE-i were also compared at pH 5 and 9, respectively. CLE-2 had the highest uptake of PNP (Qm=1.22 × 10(-1)mmol/g, pH 9) and S1 (Qm=4.27 mg/g) while cellulose and CLE-4 had the strongest binding affinity (1.43 L/mmol and 5.90 × 10(-2)L/mg), respectively. Uptake of PNP by CLE-0.5 at pH 5 (Q m=5.30 × 10(-2)mmol/g) was higher than uptake at pH 9 (Qm=3.11 × 10(-2)mmol/g). Sorption of CLE-4 with S1, S2 and S3 showed that relative uptake of the surrogates had the following order: S3>S2>S1, where S2 had the strongest binding affinity to CLE-i. CLE-2 had the highest sorption capacity towards Si in an equimolar mixture with evidence of molecular selective uptake. At pH 9, low uptake was mainly related to electrostatic repulsion between the negatively charged sorbent surface and the carboxylate head groups of Si

  7. 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.

  8. Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

    PubMed

    Yu, Honglian; Merib, Josias; Anderson, Jared L

    2016-03-18

    Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. PMID:26896916

  9. 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.

  10. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich`s solution and analysis.

  11. Inorganic-organic composite solid polymer electrolytes

    SciTech Connect

    Abraham, K.M.; Koch, V.R.; Blakley, T.J.

    2000-04-01

    Inorganic-organic composite solid polymer electrolytes (CSPEs) have been prepared from the poly(ethylene oxide) (PEO)-like electrolytes of the general formula polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-PEO{sub n}-LiX and Li{sup +}-conducting ceramic powders. In the PEO-like electrolytes, PVdF-HFP is the copolymer of PVdF and HFP, PEO{sub n} is a nonvolatile oligomeric polyethylene oxide of {approximately}400 g/mol molecular weight, and LiX is lithium bis(trifluoroethylsulfonyl)imide. Two types of inorganic oxide ceramic powders were used: a highly Li{sup +}-conducting material of the composition 14 mol % Li{sub 2}O-9Al{sub 2}O{sub 3}-38TiO{sub 2}-39P{sub 2}O{sub 5}, and the poorly Li{sup +}-conducting Li-silicates Li{sub 4{minus}x}M{sub x}SiO{sub 4} where M is Ca or Mg and x is 0 or 0.05. The composite electrolytes can be prepared as thin membranes in which the Li{sup +} conductivity and good mechanical strength of the Li{sup +}-conducting inorganic ceramics are complemented by the structural flexibility and high conductivity of organic polymer electrolytes. Excellent electrochemical and thermal stabilities have been demonstrated for the electrolyte films. Li//composite electrolyte//LiCoO{sub 2} rechargeable cells have been fabricated and cycled at room temperature and 50 C.

  12. Effect of reactive species on surface crosslinking of plasma-treated polymers investigated by surface force microscopy

    SciTech Connect

    Tajima, S.; Komvopoulos, K.

    2006-09-18

    Polymer surface modification by ions, uncharged particles, and photons of inductively coupled Ar plasma was investigated with a surface force microscope. Optical windows consisting of crystals with different cutoff wavelengths and a metal shield were used to deconvolute the effects of the various plasma species on the modification of the surface nanomechanical properties of polyethylene. The extent of surface crosslinking was related to the frictional energy dissipated during nanoscratching. It is shown that surface crosslinking is primarily due to the simultaneous effects of uncharged particles and vacuum ultraviolet photons, while the ion bombardment effect is secondary.

  13. Prediction of crosslink density of solid propellant binders. [curing of elastomers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr.

    1976-01-01

    A quantitative theory is outlined which allows calculation of crosslink density of solid propellant binders from a small number of predetermined parameters such as the binder composition, the functionality distributions of the ingredients, and the extent of the curing reaction. The parameter which is partly dependent on process conditions is the extent of reaction. The proposed theoretical model is verified by independent measurement of effective chain concentration and sol and gel fractions in simple compositions prepared from model compounds. The model is shown to correlate tensile data with composition in the case of urethane-cured polyether and certain solid propellants. A formula for the branching coefficient is provided according to which if one knows the functionality distributions of the ingredients and the corresponding equivalent weights and can measure or predict the extent of reaction, he can calculate the branching coefficient of such a system for any desired composition.

  14. Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

    NASA Astrophysics Data System (ADS)

    Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2015-09-01

    Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10-4 S cm-1 at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increase with the ionic liquid ratio.

  15. Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

    SciTech Connect

    Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2015-09-25

    Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increase with the ionic liquid ratio.

  16. AIE-Active Tetraphenylethylene Cross-Linked N-Isopropylacrylamide Polymer: A Long-Term Fluorescent Cellular Tracker.

    PubMed

    Ma, Hengchang; Qi, Chunxuan; Cheng, Chao; Yang, Zengming; Cao, Haiying; Yang, Zhiwang; Tong, Jinhui; Yao, Xiaoqiang; Lei, Ziqiang

    2016-04-01

    There is a great demand to understand cell transplantation, migration, division, fusion, and lysis. Correspondingly, illuminant object-labeled bioprobes have been employed as long-term cellular tracers, which could provide valuable insights into detecting these biological processes. In this work, we designed and synthesized a fluorescent polymer, which was comprised of hydrophilic N-isopropylacrylamide polymers as matrix and a hydrophobic tetraphenylethene (TPE) unit as AIE-active cross-linkers (DDBV). It was found that when the feed molar ratio of N-isopropylacrylamides to cross-linkers was 22:1, the produced polymers demonstrated the desirable LCST at 37.5 °C. And also, the temperature sensitivity of polymers could induce phase transfer within a narrow window (32-38 °C). Meanwhile, phase transfer was able to lead the florescent response. And thus, we concluded that two responses occur when one stimulus is input. Therefore, the new cross-linker of DDBV rendered a new performance from PNIPAm and a new chance to create new materials. Moreover, the resulted polymers demonstrated very good biocompatibility with living A549 human lung adenocarcinoma cells and L929 mouse fibroblast cells, respectively. Both of these cells retained very active viabilities in the concentration range of 7.8-125 μL/mg of polymers. Notably, P[(NIPAm)22-(DDBV)1] (P6) could be readily internalized by living cells with a noninvasive manner. The cellular staining by the fluorescent polymer is so indelible that it enables cell tracing for at least 10 passages. PMID:26966832

  17. Influence of mobile phase composition and cross-linking density on the enantiomeric recognition properties of molecularly imprinted polymers.

    PubMed

    Yu, C; Mosbach, K

    2000-08-01

    A series of experiments were conducted to investigate elements which affect the enantiomeric recognition properties of molecularly imprinted polymers (MIPs) in the HPLC mode. Our results show that the recognition properties of MIPs are greatly influenced by the mobile phase used. For a polymer prepared in acetonitrile, a good enantiomeric separation was observed when acetonitrile-based mobile phase was used, when the mobile phase was changed to chloroform-based, no enantiomeric recognition was observed although the sample molecule was retarded. This indicates that the specific co-operative binding interactions between the functional groups at the imprinted polymer's recognition sites and the sample molecule were considerably disrupted and only non-specific interactions remained. When the mobile phase was changed back to acetonitrile-based, the recognition was regained. In contrast, for polymers prepared in chloroform, chloroform-based mobile phase gave much better separation than acetonitrile-based mobile phase. When other solvents were tested, significant solvent effects were generally observed. Based on these observations, the recognition properties of the methacrylic acid (MAA)-co-ethylene glycol dimethacrylate (EGDMA) polymers were reinvestigated, and the results show that by simply using an optimised mobile phase system, significantly improved recognition over previously reported results was observed. For a polymer made against Cbz-L-Trp, 100 microg of Cbz-D,L-Trp was separated with a separation factor (alpha) of 4.23 and a resolution (Rs) of 3.87, whereas in the previous report, 10 microg of Cbz-D,L-Trp was only separated with alpha = 1.67 and Rs = 0.1. It is generally realised that the imprinted polymer's recognition property is also very much influenced by the nature of the polymer network. It was shown that the recognition decreased with a decrease in the apparent degree of cross-linking (molar percentage of cross-linker in the polymerisation mixture

  18. Solid electrolyte material manufacturable by polymer processing methods

    DOEpatents

    Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

    2012-09-18

    The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

  19. Nonlinear viscoelasticity and relaxation phenomena of polymer solids

    NASA Technical Reports Server (NTRS)

    Peng, S. T. J.; Landel, R. F.; Valanis, K. C.

    1977-01-01

    In the light of a three-chain model of statistical network theories of rubberlike elastic models, it is assumed that the free energy function of incompressible viscoelastic polymer solids is a separable, symmetric function of the principle stretch ratios and the hidden thermodynamic coordinates along the same directions. This assumption leads to a characterization of those viscoelastic polymer solids which exhibit the property of factorizability between the time and strain functions.

  20. [Preparation of a novel polymer monolith using atom transfer radical polymerization method for solid phase extraction].

    PubMed

    Shen, Ying; Qi, Li; Qiao, Juan; Mao, Lanqun; Chen, Yi

    2013-04-01

    In this study, a novel polymer monolith based solid phase extraction (SPE) material has been prepared by two-step atom transfer radical polymerization (ATRP) method. Firstly, employing ethylene glycol dimethacrylate (EDMA) as a cross-linker, a polymer monolith filled in a filter head has been in-situ prepared quickly under mild conditions. Then, the activators generated by electron transfer ATRP (ARGET ATRP) was used for the modification of poly(2-(dimethylamino)ethyl-methacrylate) (PDMAEMA) on the monolithic surface. Finally, this synthesized monolith for SPE was successfully applied in the extraction and enrichment of steroids. The results revealed that ATRP can be developed as a facile and effective method with mild reaction conditions for monolith construction and has the potential for preparing monolith in diverse devices. PMID:23898628

  1. On the Influence of Crosslinker on Template Complexation in Molecularly Imprinted Polymers: A Computational Study of Prepolymerization Mixture Events with Correlations to Template-Polymer Recognition Behavior and NMR Spectroscopic Studies

    PubMed Central

    Shoravi, Siamak; Olsson, Gustaf D.; Karlsson, Björn C. G.; Nicholls, Ian A.

    2014-01-01

    Aspects of the molecular-level basis for the function of ethylene glycol dimethacrylate and trimethylolproprane trimethacrylate crosslinked methacrylic acid copolymers molecularly imprinted with (S)-propranolol have been studied using a series of all-component and all-atom molecular dynamics studies of the corresponding prepolymerization systems. The crosslinking agents were observed to contribute to template complexation, and the results were contrasted with previously reported template-recognition behavior of the corresponding polymers. Differences in the extent to which the two crosslinkers interacted with the functional monomer were identified, and correlations were made to polymer-ligand recognition behavior and the results of nuclear magnetic resonance spectroscopic studies studies. This study demonstrates the importance of considering the functional monomer–crosslinker interaction when designing molecularly imprinted polymers, and highlights the often neglected general contribution of crosslinker to determining the nature of molecularly imprinted polymer-template selectivity. PMID:24927149

  2. 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

  3. Ionically Cross-Linked Polymer Networks for the Multiple-Month Release of Small Molecules.

    PubMed

    Lawrence, Patrick G; Patil, Pritam S; Leipzig, Nic D; Lapitsky, Yakov

    2016-02-01

    Long-term (multiple-week or -month) release of small, water-soluble molecules from hydrogels remains a significant pharmaceutical challenge, which is typically overcome at the expense of more-complicated drug carrier designs. Such approaches are payload-specific and include covalent conjugation of drugs to base materials or incorporation of micro- and nanoparticles. As a simpler alternative, here we report a mild and simple method for achieving multiple-month release of small molecules from gel-like polymer networks. Densely cross-linked matrices were prepared through ionotropic gelation of poly(allylamine hydrochloride) (PAH) with either pyrophosphate (PPi) or tripolyphosphate (TPP), all of which are commonly available commercial molecules. The loading of model small molecules (Fast Green FCF and Rhodamine B dyes) within these polymer networks increases with the payload/network binding strength and with the PAH and payload concentrations used during encapsulation. Once loaded into the PAH/PPi and PAH/TPP ionic networks, only a few percent of the payload is released over multiple months. This extended release is achieved regardless of the payload/network binding strength and likely reflects the small hydrodynamic mesh size within the gel-like matrices. Furthermore, the PAH/TPP networks show promising in vitro cytocompatibility with model cells (human dermal fibroblasts), though slight cytotoxic effects were exhibited by the PAH/PPi networks. Taken together, the above findings suggest that PAH/PPi and (especially) PAH/TPP networks might be attractive materials for the multiple-month delivery of drugs and other active molecules (e.g., fragrances or disinfectants). PMID:26811936

  4. Photoinduced bending behavior of cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone.

    PubMed

    Lv, Jiu-an; Wang, Weiru; Xu, Jixiang; Ikeda, Tomiki; Yu, Yanlei

    2014-07-01

    Cross-linked azobenzene liquid-crystalline polymer films with a poly(oxyethylene) backbone are synthesized by photoinitiated cationic copolymerization. Azobenzene moieties in the film surface toward the light source are simultaneously photoaligned during photopolymerization with unpolarized 436 nm light and thus form a splayed alignment in the whole film. The prepared films show reversible photoinduced bending behavior with opposite bending directions when different surfaces of one film face to ultraviolet light irradiation. PMID:24771514

  5. Surface morphological modification of crosslinked hydrophilic co-polymers by nanosecond pulsed laser irradiation

    NASA Astrophysics Data System (ADS)

    Primo, Gastón A.; Alvarez Igarzabal, Cecilia I.; Pino, Gustavo A.; Ferrero, Juan C.; Rossa, Maximiliano

    2016-04-01

    This work reports an investigation of the surface modifications induced by irradiation with nanosecond laser pulses of ultraviolet and visible wavelengths on crosslinked hydrophilic co-polymeric materials, which have been functionalized with 1-vinylimidazole as a co-monomer. A comparison is made between hydrogels differing in the base co-monomer (N,N-dimethylaminoethyl methacrylate and N-[3-(dimethylamino)propyl] methacrylamide) and in hydration state (both swollen and dried states). Formation of craters is the dominant morphological change observed by ablation in the visible at 532 nm, whereas additional, less aggressive surface modifications, chiefly microfoams and roughness, are developed in the ultraviolet at 266 nm. At both irradiation wavelengths, threshold values of the incident laser fluence for the observation of the various surface modifications are determined under single-pulse laser irradiation conditions. It is shown that multiple-pulse irradiation at 266 nm with a limited number of laser shots can be used alternatively for generating a regular microfoam layer at the surface of dried hydrogels based on N,N-dimethylaminoethyl methacrylate. The observations are rationalized on the basis of currently accepted mechanisms for laser-induced polymer surface modification, with a significant contribution of the laser foaming mechanism. Prospective applications of the laser-foamed hydrogel matrices in biomolecule immobilization are suggested.

  6. Optimization of β-cyclodextrin cross-linked polymer for monitoring of quercetin

    NASA Astrophysics Data System (ADS)

    Zhu, Xiashi; Ping, Wenhui

    2014-11-01

    A novel method for the separation/analysis of quercetin was described, which was based on the investigation of the inclusion interactions of β-cyclodextrin cross-linked polymer (β-CDCP) with quercetin (Qu) and the adsorption behavior of Qu on β-CDCP. The inclusion interaction of β-CDCP with Qu was studied through FTIR, TGA and 13C NMR. Under the optimum conditions, the preconcentration factor of the proposed method was approximately 8.8, the β-CDCP could be used repeatedly for 30 times and offered better recovery. The linear range, limit of detection (LOD) and the relative standard deviation (RSD) was found to be 0.10-12.0 μg mL-1, 4.6 ng mL-1 and 3.10% (n = 3, c = 2.0 μg mL-1) respectively. This technique had been successfully applied to the determination of Qu in real samples.

  7. High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks

    PubMed Central

    Liu, Bo; Png, Rui-Qi; Zhao, Li-Hong; Chua, Lay-Lay; Friend, Richard H.; Ho, Peter K.H.

    2012-01-01

    The power conversion efficiency of organic photovoltaic cells depends crucially on the morphology of their donor–acceptor heterostructure. Although tremendous progress has been made to develop new materials that better cover the solar spectrum, this heterostructure is still formed by a primitive spontaneous demixing that is rather sensitive to processing and hence difficult to realize consistently over large areas. Here we report that the desired interpenetrating heterostructure with built-in phase contiguity can be fabricated by acceptor doping into a lightly crosslinked polymer donor network. The resultant nanotemplated network is highly reproducible and resilient to phase coarsening. For the regioregular poly(3-hexylthiophene):phenyl-C61-butyrate methyl ester donor–acceptor model system, we obtained 20% improvement in power conversion efficiency over conventional demixed biblend devices. We reached very high internal quantum efficiencies of up to 0.9 electron per photon at zero bias, over an unprecedentedly wide composition space. Detailed analysis of the power conversion, power absorbed and internal quantum efficiency landscapes reveals the separate contributions of optical interference and donor–acceptor morphology effects. PMID:23271655

  8. Highly Stable and Porous Cross-Linked Polymers for Efficient Photocatalysis

    SciTech Connect

    Xie, Zhigang; Wang, Cheng; deKrafft, Kathryn E.; Lin, Wenbin

    2011-02-23

    Porous cross-linked polymers (PCPs) with phosphorescent [Ru(bpy)₃]{sup 2+} and [Ir(ppy)₂(bpy)]{sup +} building blocks were obtained via octacarbonyldicobalt (Co₂(CO)₈)-catalyzed alkyne trimerization reactions. The resultant Ru- and Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m²/g, respectively. They are thermally stable at up to 350 °C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, α-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous [Ru(bpy)₃]{sup 2+} and [Ir(ppy)₂(bpy)]{sup +} photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations.

  9. Plasticization and crosslinking effects of acetone-formaldehyde and tannin resins on wheat protein-based natural polymers.

    PubMed

    Zhang, Xiaoqing; Do, My Dieu

    2009-07-01

    Efficient plasticization and sufficient crosslinking were achieved by using an acetone-formaldehyde (AF) resin as an additive in the thermal processing of wheat protein-based natural polymers. The mobile AF resin and its strong intermolecular interactions with a wheat protein matrix produced sufficient flexibility for the plastics, while the covalent bonds formed between AF and the protein chains also caused the water-soluble resin to be retained in the materials under wet conditions. The mechanical properties of the materials were also enhanced as an additional benefit due to the formation of crosslinked networks through the polymer matrix. Tensile strength was further enhanced when using AF in conjunction with tannin resin (AFTR) in the systems as rigid aromatic structures were formed in the crosslinking segments. Different components in wheat proteins (WPs) or wheat gluten (WG) (e.g., proteins, residual starch and lipids) displayed different capabilities in interaction and reaction with the AFTR additives, and thus resulted in different performances when the ratio of these components varied in the materials. The application of the AFTR additives provides a feasible methodology to thermally process wheat protein-based natural polymers with improved mechanical performance and water-resistant properties. PMID:19447383

  10. New Solid Polymer Electrolytes for Improved Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Hehemann, David G.

    2002-01-01

    The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

  11. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes

    SciTech Connect

    Tenhaeff, Wyatt E; Yu, Xiang; Hong, Kunlun; Perry, Kelly A; Dudney, Nancy J

    2011-01-01

    A study of lithium cation transport across solid-solid electrolyte interfaces to identify critical resistances in nanostructured solid electrolytes is reported. Bilayers of glass and polymer thin film electrolytes were fabricated and characterized for this study. The glass electrolyte was lithium phosphorous oxynitride (Lipon), and two polymer electrolytes were studied: poly(methyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) and poly(styrene-co-poly(ethylene glycol) methyl ether methacrylate). Both copolymers contained LiClO{sub 4} salt. In bilayers where polymer electrolyte layers are fabricated on top of Lipon, the interfacial resistance dominates transport. At 25 C, the interfacial resistance is at least three times greater than the sum of the Lipon and polymer electrolyte resistances. By reversing the structure and fabricating Lipon on top of the polymer electrolytes, the interfacial resistance is eliminated. Experiments to elucidate the origin of the interfacial resistance in the polymer-on-Lipon bilayers reveal that the solvent mixtures used to fabricate the polymer layers do not degrade the Lipon layer. The importance of the polymer electrolytes' mechanical properties is also discussed.

  12. 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.

  13. Reversible cross-linking, microdomain structure, and heterogeneous dynamics in thermally reversible cross-linked polyurethane as revealed by solid-state NMR.

    PubMed

    Zhang, Rongchun; Yu, Shen; Chen, Shengli; Wu, Qiang; Chen, Tiehong; Sun, Pingchuan; Li, Baohui; Ding, Datong

    2014-01-30

    Polyurethane material is widely utilized in industry and daily life due to its versatile chemistry and relatively easy handling. Here, we focused on a novel thermally reversible cross-linked polyurethane with comprehensive remarkable mechanical properties as reported in our recent work (Adv. Mater. 2013, 25, 4912). The microphase-separated structure and heterogeneous segmental dynamics were well revealed by T2 relaxometry experiments, which was also first utilized to in situ monitor the reversible cross-linking associated with Diels-Alder (DA) and retro-Diels-Alder (RDA) reactions. On the basis of T2 relaxometry results, we determined the actual temperature of the (R)DA reaction as well as the corresponding activation energies of the motion of soft segments. Besides, the roles of the temperature and cross-linker contents on the microdomain structure and dynamics are discussed in detail. It is found that the microphase separation is enhanced by the increase of temperature as well as the incorporation of cross-linkers. Also, the polyurethane samples are still thermal-stable even at a high temperature beyond the disassociation of the cross-linkages. Furthermore, Baum-Pines and three-pulse multiple-quantum NMR experiments are utilized to investigate the heterogeneous structures and dynamics of the mobile and rigid segments, respectively. Both the results obtained from the T2 relaxometry and multiple-quantum NMR experiments are in good agreement with the macroscopic mechanical properties of the polyurethane. Finally, it is also well demonstrated that proton T2 relaxometry combined with multiple-quantum NMR is a powerful method to study the heterogeneous structures and dynamics of a multiphase polymer system. PMID:24400980

  14. 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.

  15. Solid polymer electrolytes for rechargeable batteries. Final report

    SciTech Connect

    Narang, S.C.; Ventura, S.C.

    1992-02-01

    SRI International has synthesized and tested new, dimensionally stable polymer electrolytes for high energy density rechargeable lithium batteries. We have prepared semi-interpenetrating networks of sulfur-substituted polyethyleneoxide with tetmethylorthosilicate (TEOS). The in situ hydrolysis of TEOS produces a mechanically stable three-dimensional network that entangles the polymer electrolytes and makes the film dimensionally flexible and stable. With this approach, the best dimensionally stable polymer electrolyte of this type produced so far, has a room temperature lithium ion conductivity of 7.5 {times} 10{sup {minus}4} S cm{sup {minus}1}. Another type of solid polymer electrolytes, polydiacetylene-based single-ion conductors with high room temperature proton conductivity were also developed. The best conductivity of these polymers is two orders of magnitude higher than that of Nafion under comparable experimental conditions. With further appropriate chemical modification, the new polymers could be used in fuel cells.

  16. Removal of highly crosslinked resists and hybrid polymers for single micro parts fabrication and nanoimprint stamp rework

    NASA Astrophysics Data System (ADS)

    Voigt, Anja; Engelke, Rainer; Ahrens, Gisela; Bullerjahn, Franziska; Schleunitz, Arne; Klein, Jan J.; Grützner, Gabi

    2014-03-01

    Thick photoresists, e.g. up to 1 mm layer thickness, are widely used for the manufacture of high aspect ratio microstructures, e.g. as mould for the fabrication of metallic micro parts. Such resists or materials exhibit high mechanical and chemical stability to non-deformably withstand a pattern transfer process, e.g. by electroplating. After the pattern transfer a solvent based removal is difficult or not possible in many cases. A selective mould removal - without the damage of electroplated metal structures - is required for the fabrication of single micro parts. As second application example UV curable and strongly crosslinkable inorganic-organic hybrid polymers such as OrmoComp ® and OrmoStamp ® are used in UV moulding. The cleaning and rework of these moulds or also of stamps for nanoimprint lithography (NIL) is a challenging task with increasing importance. The life time of an expensive master mould or stamp as well as of the replicated working stamps is important, and therefore the ability to rework such stamps without any defect or decreased resolution. Hence, we demonstrate the application of a plasma-assisted removal using the STP 2020 etching tool from MUEGGE [1] for remote dry etching of strongly crosslinked materials, i.e. the development of processes for the isotropical etching of highly crosslinked photoresists and hybrid polymer materials will be presented. In combination with this specific etching tool this technique shows a high potential to make plasma-assisted removal ready for industrial production.

  17. Solid polymer battery electrolyte and reactive metal-water battery

    DOEpatents

    Harrup, Mason K.; Peterson, Eric S.; Stewart, Frederick F.

    2000-01-01

    In one implementation, a reactive metal-water battery includes an anode comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

  18. Preparation of redox polymer cathodes for thin film rechargeable batteries

    DOEpatents

    Skotheim, Terje A.; Lee, Hung S.; Okamoto, Yoshiyuki

    1994-11-08

    The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

  19. Silicone oil emulsions stabilized by polymers and solid particles.

    PubMed

    Kawaguchi, Masami

    2016-07-01

    Silicone oil emulsions stabilized by various emulsifiers such as polymers, solid particles alone, and solid particles with pre-adsorbed surfactants or polymers are reviewed, focusing on their emulsion stability and rheological properties as a function of the emulsifier concentration. An increase in the concentration of the emulsifier leads to a decrease in the droplet size and an increase in the emulsion stability, irrespective of the emulsifier. Moreover, the overlapping concentration of polymer can be regarded as a criterion for the preparation of emulsions using polymeric emulsifiers. Changes in the emulsion stability and rheological responses of the emulsions prepared by the solid particles with pre-adsorbed polymers are discussed in terms of the amounts of the emulsifiers adsorbed. For emulsions prepared from hydrophilic silica particles with pre-adsorbed polymers, a decrease in the droplet size of an order of magnitude can be controlled by an increase in the concentration of polymer, whereas hydrophilic silica particles alone cannot produce stable silicone oil emulsions. PMID:26170165

  20. Solid Rocket Fuel Constitutive Theory and Polymer Cure

    NASA Technical Reports Server (NTRS)

    Ream, Robert

    2006-01-01

    Solid Rocket Fuel is a complex composite material for which no general constitutive theory, based on first principles, has been developed. One of the principles such a relation would depend on is the morphology of the binder. A theory of polymer curing is required to determine this morphology. During work on such a theory an algorithm was developed for counting the number of ways a polymer chain could assemble. The methods used to develop and check this algorithm led to an analytic solution to the problem. This solution is used in a probability distribution function which characterizes the morphology of the polymer.

  1. Solid Polymer Electrolyte (SPE) fuel cell technology program

    NASA Technical Reports Server (NTRS)

    1979-01-01

    The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

  2. Effect of Cross-Linking on the Structure and Growth of Polymer Films Prepared by Interfacial Polymerization.

    PubMed

    Berezkin, Anatoly V; Kudryavtsev, Yaroslav V

    2015-11-10

    Interfacial polymerization of tri- and bifunctional monomers (A3B2 polymerization) is investigated by dissipative particle dynamics to reveal an effect of cross-linking on the reaction kinetics and structure of the growing polymer film. Regardless of the comonomer reactivity and miscibility, the kinetics in an initially bilayer melt passes from the reaction to diffusion control. Within the crossover period, branched macromolecules undergo gelation, which drastically changes the scenario of the polymerization process. Comparison with the previously studied linear interfacial polymerization (Berezkin, A. V.; Kudryavtsev, Y. V. Linear Interfacial Polymerization: Theory and Simulations with Dissipative Particle Dynamics J. Chem. Phys. 2014, 141, 194906) shows similar conversion rates but very different product characteristics. Cross-linked polymer films are markedly heterogeneous in density, their average polymerization degree grows with the comonomer miscibility, and end groups are mostly trapped deeply in the film core. Products of linear interfacial polymerization demonstrate opposite trends as they are spontaneously homogenized by a convective flow of macromolecules expelled from the reactive zone to the film periphery, which we call the reactive extrusion effect and which is hampered in branched polymerization. Influence of the comonomer architecture on the polymer film characteristics could be used in various practical applications of interfacial polymerization, such as fabrication of membranes, micro- and nanocapsules and 3D printing. PMID:26471239

  3. [Preparation and application of solid phase extraction packing of zirconia microsphere coated with sulfonated crosslinked polystyrene].

    PubMed

    Shen, Shuchang; Liu, Yuhui; Xiao, Xiaoxing

    2013-08-01

    Zirconia microsphere was prepared by polymerization-induced colloid aggregation (PICA) method and carbon-carbon double bond was grafted onto its surface by titanic acid ester coupling reagent. Poly(styrene-divinylbenzene) was synthesized by free radical polymerization by using styrene, divinylbenzene and carbon-carbon double bond on the microsphere surface in solution system, so the polymer was coated on the microsphere surface. After the benzene ring of the polymer was sulfonated, the cation exchange packing for solid phase extraction (SPE) was obtained. The material was characterized by Fourier transform infrared spectroscopy, scanning electron microscope and X-ray energy dispersive spectroscopy. Three herbicides of mesotrione, atrazine and acetochlor in water were determined by the SPE cartridge coupled with high performance liquid chromatography (HPLC). In the range of 0.5 - 3.0 mg/L, the relationships between the peak areas and mass concentrations of mesotrione, atrazine and acetochlor were linear with the correlation coefficients of 0.9936, 0.9925, 0.9919, respectively. The limits of detection were 5.41, 6.72 and 13.4 microg/L for mesotrione, atrazine and acetochlor, respectively. The results showed that the zirconium dioxide microspheres coated with polymer have diameters in the range of about 6 to 8 microm, the SPE cartridges of which have high adsorption rate for the targets. PMID:24369611

  4. Cross-Linked Conjugated Polymer Fibrils: Robust Nanowires from Functional Polythiophene Diblock Copolymers

    SciTech Connect

    Hammer, Brenton A. G.; Bokel, Felicia A.; Hayward, Ryan C.; Emrick, Todd

    2011-09-27

    A series of poly(3-hexyl thiophene) (P3HT)-based diblock copolymers were prepared and examined in solution for their assembly into fibrils, and post-assembly cross-linking into robust nanowire structures. P3HT-b-poly(3-methanol thiophene) (P3MT), and P3HT-b-poly(3-aminopropyloxymethyl thiophene) (P3AmT) diblock copolymers were synthesized using Grignard metathesis (GRIM) polymerization. Fibrils formed from solution assembly of these copolymers are thus decorated with hydroxyl and amine functionality, and cross-linking is achieved by reaction of diisocyanates with the hydroxyl and amine groups. A variety of cross-linked structures, characterized by transmission electron microscopy (TEM), were produced by this method, including dense fibrillar sheets, fibril bundles, or predominately individual fibrils, depending on the chosen reaction conditions. In solution, the cross-linked fibrils maintained their characteristic vibronic structure in solvents that would normally disrupt (dissolve) the structures.

  5. Elastin-Mimetic Protein Polymers Capable of Physical and Chemical Crosslinking

    PubMed Central

    Sallach, Rory E.; Cui, Wanxing; Wen, Jing; Martinez, Adam; Conticello, Vincent P.; Chaikof, Elliot L.

    2008-01-01

    We report the synthesis of a new class of recombinant elastin-mimetic triblock copolymer capable of both physical and chemical crosslinking. These investigations were motivated by a desire to capture features unique to both physical and chemical crosslinking schemes so as to exert optimal control over a wide range of potential properties afforded by protein-based mutiblock materials. We postulated that by chemically locking a multiblock protein assembly in place, functional responses that are linked to specific domain structures and morphologies may be preserved over a broader range of loading conditions that would otherwise disrupt microphase structure solely stabilized by physical crosslinking. Specifically, elastic modulus was enhanced and creep strain reduced through the addition of chemical crosslinking sites. Additionally, we have demonstrated excellent in vivo biocompatibility of glutaraldehyde treated multiblock systems. PMID:18954902

  6. Synthesis and application of cephalexin imprinted polymer for solid phase extraction in milk.

    PubMed

    Lata, Kiran; Sharma, Rajan; Naik, Laxmana; Rajput, Y S; Mann, Bimlesh

    2015-10-01

    Molecular imprinted polymer (MIP) against cephalexin was synthesized by co-polymerization of functional monomer, cross-linker, radical initiator, along with target molecule (cephalexin) in a porogenic material. Binding of cephalexin towards prepared MIP was studied in different solvents (water, methanol, 1M NaCl, acetone and acetonitrile) and best binding was observed in methanol. Partition coefficient and selectivity of prepared imprint and non-imprint was also studied. Cross reactivity in terms of binding efficiency was also assessed with other antibiotics. Chromatographic study of MIP was carried out by packing prepared imprint into glass column. MIP was used as matrix in solid phase extraction (SPE) for recovery of cephalexin from spiked milk samples for further estimation by high performance liquid chromatography. No interference was observed from milk components after elution of cephalexin from MIP, indicating selectivity and affinity of MIP. On the other hand, interference was observed in eluate obtained from C18 SPE column. PMID:25872441

  7. Water-compatible molecularly imprinted polymers for selective solid phase extraction of dencichine from the aqueous extract of Panax notoginseng.

    PubMed

    Ji, Wenhua; Xie, Hongkai; Zhou, Jie; Wang, Xiao; Ma, Xiuli; Huang, Luqi

    2016-01-01

    Specific molecularly imprinted polymers for dencichine were developed for the first time in this study by the bulk polymerization using phenylpyruvic acid and dl-tyrosine as multi-templates. The photographs confirmed that molecularly imprinted polymers prepared using N,N'-methylene diacrylamide as cross-linker and glycol dimethyl ether as porogen displayed excellent hydrophilicity. Selectivity, adsorption isotherm and adsorption kinetics were investigated. The sample loading-washing-eluting solvent was optimized to evaluate the property of molecularly imprinted solid phase extract. Compared with LC/WCX-SPE, water-compatible molecularly imprinted solid phase extraction displayed more excellent specific adsorption performance. The extracted dencichine from Panax notoginseng with the purity of 98.5% and the average recovery of 85.6% (n=3) was obtained. PMID:26680322

  8. Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

    NASA Technical Reports Server (NTRS)

    Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

    2003-01-01

    This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

  9. Oil and fat absorbing polymers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr. (Inventor)

    1977-01-01

    A method is described for forming a solid network polymer having a minimal amount of crosslinking for use in absorbing fats and oils. The polymer remains solid at a swelling ratio in oil or fat of at least ten and provides an oil absorption greater than 900 weight percent.

  10. An automated spin-assisted approach for molecular layer-by-layer assembly of crosslinked polymer thin films

    SciTech Connect

    Chan, Edwin P.; Chung, Jun Young; Stafford, Christopher M.; Lee, Jung-Hyun

    2012-11-15

    We present the design of an automated spin-coater that facilitates fabrication of polymer films based on molecular layer-by-layer (mLbL) assembly. Specifically, we demonstrate the synthesis of ultrathin crosslinked fully-aromatic polyamide (PA) films that are chemically identical to polymer membranes used in water desalination applications as measured by X-ray photoelectron spectroscopy. X-ray reflectivity measurements indicate that the automated mLbL assembly creates films with a constant film growth rate and minimal roughness compared with the traditional interfacial polymerization of PA. This automated spin-coater improves the scalability and sample-to-sample consistency by reducing human involvement in the mLbL assembly.

  11. Fabrication and characterization of solid-state, conducting polymer actuators

    SciTech Connect

    Xie, J.; Sansinena, J. M.; Gao, J.; Wang, H. L.

    2004-01-01

    We report here the fabrication and characterization of solid-state, conducting polymer actuators. The electrochemical activity of polyaniline (PANI) thin film coated with solid-state polyelectrolyte is very similar to the polyaniline thin film in an aqueous solution. The solid-state actuator is adhere to a lever arm of an force transducer and the force generation is measured in real time. The force generated by the actuator is found to be length dependent. However, the overall torques generated by the actuators with different lengths remains essentially the same. The effect of stimulation signals such as voltage, current, on the bending angle and displacement is also studied using square wave potential.

  12. Preparation and characterization of cross-linked collagen-phospholipid polymer hybrid gels.

    PubMed

    Nam, Kwangwoo; Kimura, Tsuyoshi; Kishida, Akio

    2007-01-01

    2-methacryloyloxyethyl phosphorylcholine (MPC)-immobilized collagen gel was developed. Using 1-ethyl-3-(3-dimethyl aminopropyl)-1-carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), we cross-linked a collagen film in 2-morpholinoethane sulfonic acid (MES) buffer (EN gel). EN gel was prepared under both pH 4.5 and pH 9.0 in order to observe changes in cross-linking ability. To cross-link MPC to collagen gel, poly(MPC-co-methacrylic acid) (PMA) having a carboxyl group side chain was chosen. E/N gel was added to the MES buffer having pre-NHS activated PMA to make MPC-immobilized collagen gel (MiC gel). MiC gel was prepared under both acidic and alkaline conditions to observe the changes in the cross-linking ability of PMA. X-ray photoelectron spectroscopy showed that the PMA was cross-linked with collagen under both acidic and alkaline conditions. Differential scanning calorimetry (DSC) results showed that the shrinkage temperature increased for the MiC gels and that the increase would be greater for the MiC gel prepared under alkaline conditions. The data showed that swelling would be less when the MiC gel was prepared under alkaline conditions. The biodegradation caused by collagenase was suppressed for the MiC gel prepared under alkaline conditions due to stable inter- and intrahelical networks. PMID:16959313

  13. Synthesis, characterization and biocompatibility of novel biodegradable cross-linked co-polymers based on poly(propylene oxide) diglycidylether and polyethylenimine.

    PubMed

    Ding, Yunsheng; Wang, Jing; Wong, Cynthia S; Halley, Peter J; Guo, Qipeng

    2011-01-01

    Novel biodegradable cross-linked co-polymers were prepared from poly(propylene glycol) diglycidylether (PPGDGE) and poly(ethylene imine) (PEI). PPGDGE and PEI were mixed at ambient temperature with varying PEI concentrations of 10, 15, 18.5, 25, 30, 40 and 50 wt%; the homogenous PPGDGE/PEI mixtures obtained were cured at elevated temperatures, resulting in formation of PPG-PEI cross-linked co-polymers via ring-opening reaction of PPGDGE with PEI. The physicochemical and biological properties of these co-polymers were dependent on the PEI content and the extent of curing reaction. The glass transition temperature of PPG-PEI cross-linked co-polymers varied in the range from -14 to +42°C, while the co-polymers displayed composition-dependent mechanical behavior, from brittle to ductile with increasing PEI content from 18.5 wt% to 40 wt%. Chinese hamster ovary (CHO) cells were cultured on the PPG-PEI co-polymers; the MTT assay was used to measure cell viability and determine the cytotoxicity. The cell viability rate, relative to tissue-culture polystyrene (TCPS), increased from 49% to 125% with increasing PEI content from 18.5 wt% to 40 wt%. Although epoxy monomers usually exhibit cytotoxicity, the epoxy groups were exhausted via curing reaction in the fully cross-linked co-polymers. The PEI-cured PPG epoxy resin, i.e., PPG-PEI cross-linked co-polymers obtained in this study, showed excellent biocompatibility. PMID:20566040

  14. Solving the Problem of Building Models of Crosslinked Polymers: An Example Focussing on Validation of the Properties of Crosslinked Epoxy Resins

    PubMed Central

    Hall, Stephen A.; Howlin, Brendan J; Hamerton, Ian; Baidak, Alex; Billaud, Claude; Ward, Steven

    2012-01-01

    The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE) and triglycidyl-p-amino phenol (TGAP) with the curing agent diamino diphenyl sulphone (DDS). The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (Tg). Typical models comprise some 4200–4600 atoms (ca. 120–130 monomers). In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA) to measure Tg. Results for the three epoxy systems yield good agreement with experimental Tg ranges of 200–220°C, 270–285°C and 285–290°C with corresponding simulated ranges of 210–230°C, 250–300°C, and 250–300°C respectively. PMID:22916182

  15. Molecularly imprinted polymers-curcuminoids and its application for solid phase extraction

    NASA Astrophysics Data System (ADS)

    Wulandari, Meyliana; Amran, M. B.; Lopez, A. B. Descalzo; Urraca, J. L.; Moreno-Bondi, M. C.

    2014-03-01

    Molecularly Imprinted Polymers (MIPs) for the selective recognition properties of curcumin (CUR), a cancer chemopreventive agent were obtained by a non-covalent imprinting approach with bisdemetoxycurcumin (BDMC) as the template molecule. The double bond of BDMC has been reduced in order not to be involved in polymerization and make the template molecules easy to be eluted. Several functional monomers have been evaluated to maximize the interactions with the template molecule during polymerization. MIPs prepared by bulk of N-(2-aminoethyl) metacrylamid hydrochlorideas functional monomer, ethylene glycol dimethacrylate as crosslinker, 2,2'-azobis (2'4-dimethyl valeronitril) as initiator and acetonitrile as porogen. Non-imprinted polymer (NIP) have been also synthesized for reference purposes. UV-vis spectroscopy has been used to predict the template to functional monomer ratio which indicates the formation of 2:1 complexes between monomer and curcumin and the association constants (K11 = 2529 μM and K12 = 1960.75 μM in acetonitrile). The capacity and imprinting factor have been evaluated as stationary phases in high-pressure liquid chromatography to CUR and BDMC. The binding properties and the homogeneity of the binding sites of the different polymers have been studied by Freundlich isotherm modeling and weight average affinity and number of binding sites. One of the foremost applications of molecular imprinting has been in molecularly imprinted solid phase extraction and it has the ability to separate and preconcentrate between closely related compounds in curcuminoids.

  16. Molecularly imprinted polymer microspheres for solid-phase extraction of protocatechuic acid in Rhizoma homalomenae.

    PubMed

    Chen, Fang-Fang; Wang, Guo-Ying; Shi, Yan-Ping

    2011-10-01

    Molecularly imprinted polymers (MIPs) had been prepared by precipitation polymerization method using acrylamide as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, acetonitrile as the porogen solvent and protocatechuic acid (PA), one of phenolic acids, as the template molecule. The MIPs were characterized by scanning electron microscopy and Fourier transform infrared, and their performance relative to non-imprinted polymers was assessed by equilibrium binding experiments. Six structurally similar phenolic acids, including p-hydroxybenzoic acid, gallic acid, salicylic acid, syringic acid, vanillic acid, ferulic acid were selected to assess the selectivity and recognition capability of the MIPs. The MIPs were applied to extract PA from the traditional Chinese medicines as a solid-phase extraction sorbent. The resultant cartridge showed that the MIPs have a good extraction performance and were able to selectively extract almost 82% of PA from the extract of Rhizoma homalomenae. Thus, the proposed molecularly imprinted-solid phase extraction-high performance liquid chromatography method can be successfully used to extract and analyse PA in traditional Chinese medicines. PMID:21809445

  17. In situ infrared spectroscopic and density-functional studies of the cross-linked structure of one-dimensional C{sub 60} polymer

    SciTech Connect

    Takashima, A.; Onoe, J.; Nishii, T.

    2010-08-15

    We have examined the infrared (IR) spectra of electron-beam (EB) irradiated C{sub 60} films, using in situ IR spectroscopy in the temperature range of 60-300 K. The irradiation-time evolution of the IR spectra shows that two highly intense new peaks finally appear around 565 and 1340 cm{sup -1} when the EB-induced C{sub 60} polymerization was saturated. To determine the cross-linked structure of the polymer explicitly, we have compared the IR spectra with theoretical spectra obtained from the cross-linked structure of all C{sub 120} stable isomers derived from the general Stone-Wales (GSW) rearrangement, using first-principles density-functional calculations. Since each C{sub 120} isomer has the same cross-linked structure as that of its corresponding one-dimensional (1D) C{sub 60} polymer, the IR modes obtained from the cross-linked structure of C{sub 120} are close to those obtained from the corresponding 1D polymer. Comparison between the experimental and theoretical IR spectra suggests that the 1D peanut-shaped C{sub 60} polymer has a cross-linked structure roughly similar to that of the P08 peanut-shaped C{sub 120} isomer.

  18. In vitro and in vivo evaluation of novel cross-linked saccharide based polymers as bile acid sequestrants.

    PubMed

    Lopez-Jaramillo, Francisco Javier; Giron-Gonzalez, Maria Dolores; Salto-Gonzalez, Rafael; Hernandez-Mateo, Fernando; Santoyo-Gonzalez, Francisco

    2015-01-01

    Bile acid sequestrants (BAS) represent a therapeutic approach for the management of hypercholesterolemia that relies on the cationic polymeric nature of BAS to selectively bind negatively charged bile acids. We hypothesized that the cross-linking of β-cyclodextrin (β-CD) and saccharides such as starch or dextrin with divinyl sulfone (DVS) yields homo- and hetero-polymeric materials with the ability to trap sterols. Our hypothesis was put to test by synthesizing a library of 22 polymers that were screened to evaluate their capability to sequester both cholesterol (CHOL) and cholic and deoxycholic acids (CA and DCA). Three polymers synthesized in high yield were identified as promising. Two were neutral hetero-polymers of β-CD and starch or dextrin and the third was a weakly cationic homo-polymer of starch, highlighting the importance of the cavity effect. They were tested in hypercholesterolemic male Wistar rats and their ability to regulate hypercholesterolemia was similar to that for the reference BAS cholestyramine, but with two additional advantages: (i) they normalized the TG level and (ii) they did not increase the creatinine level. Neither hepatotoxicity nor kidney injury was detected, further supporting them as therapeutical candidates to manage hypercholesterolemia. PMID:25719741

  19. Chemical immobilization of crosslinked polymeric ionic liquids on nitinol wires produces highly robust sorbent coatings for solid-phase microextraction.

    PubMed

    Ho, Tien D; Toledo, Bruna R; Hantao, Leandro W; Anderson, Jared L

    2014-09-16

    Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30%w/w) H2O2 solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix. PMID:25150693

  20. SRM (Solid Rocket Motor) propellant and polymer materials structural modeling

    NASA Technical Reports Server (NTRS)

    Moore, Carleton J.

    1988-01-01

    The following investigation reviews and evaluates the use of stress relaxation test data for the structural analysis of Solid Rocket Motor (SRM) propellants and other polymer materials used for liners, insulators, inhibitors, and seals. The stress relaxation data is examined and a new mathematical structural model is proposed. This model has potentially wide application to structural analysis of polymer materials and other materials generally characterized as being made of viscoelastic materials. A dynamic modulus is derived from the new model for stress relaxation modulus and is compared to the old viscoelastic model and experimental data.

  1. A hybrid solid-liquid polymer photodiode for the bioenvironment

    NASA Astrophysics Data System (ADS)

    Antognazza, M. R.; Ghezzi, D.; Musitelli, D.; Garbugli, M.; Lanzani, G.

    2009-06-01

    We demonstrate that a prototypical semiconducting polymer, poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) maintains unaltered its optoelectronic properties throughout the various steps for neural preparation. Films of MEH-PPV, after prolonged immersion in water or buffer solution, are characterized by linear and nonlinear optical spectroscopy. Based on this result, we introduce a hybrid solid-liquid photodiode based on MEH-PPV, in which we use culturing media as liquid, ionic cathodes. The hybrid device is proposed as an active interface between living tissue and conducting polymers for cell diagnostic and neural implants.

  2. 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.

  3. Quasi Solid Polymer Electrolytes for Dye Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Dissanayake, M. A. K. Lakshman

    2013-07-01

    Dye-sensitized solar cell (DSSC) has been considered as an alternative to the conventional silicon solar cell because of low cost, easy fabrication and relatively high conversion efficiency. A DSSC consists of a dye-sensitized nanoparticulated TiO2 electrode, an electrolyte containing redox couple and a Pt coated counter electrode. Such solar cells based on an I-/I3- redox couple in an organic solvent usually have conversion efficiencies reaching around 11%. However, a major drawback of these solution based solar cells, originally developed by Gratzel and coworkers is the lack of long-term stability due to liquid leakage, usage of volatile liquids such as acetonitrile, electrode corrosion, and photodecomposition of the dye in the solvent medium. Therefore considerable research efforts have been made in recent years to replace the liquid electrolytes with solid polymer or quasi-solid polymer (gel) electrolytes. Among these approaches, the use of gel polymer electrolytes appears to give rise to successful results in terms of conversion efficiency. Conventional poly (ethylene oxide)(PEO)-based solid polymer electrolytes exhibit poor ionic conductivities at room temperature, which is not sufficient for practical applications. Therefore, most of the recent studies have been directed to the preparation and characterization of gel polymer electrolytes which exhibit higher ionic conductivity at ambient temperature while maintain quai-solid structure. These gel polymer electrolytes prepared by incorporating a liquid electrolyte into a matrix polymer such as polyacrylonitrile(PAN), poly(vinylidene fluoride)(PVdF), poly (methyl methacrylate) (PMMA) and PEO have been employed in quasi-solid-state DSSCs to achieve power conversion efficiencies of more than 5%. Significant improvements have been achieved in recent years by modifications of the electrolytes by optimizing the ionic salt, introducing additives such as inorganic nanofillers, organic molecules and ionic liquids in

  4. A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems

    PubMed Central

    Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T.; Ware, Taylor; Voit, Walter E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

    2014-01-01

    The synthetic design and thermomechanical characterization of shape memory polymers (SMPs) built from a new polyurethane chemistry that enables facile, bulk and tunable cross-linking of low-molecular weight thermoplastics by electron beam irradiation is reported in this study. SMPs exhibit stimuli-induced geometry changes and are being proposed for applications in numerous fields. We have previously reported a polyurethane SMP system that exhibits the complex processing capabilities of thermoplastic polymers and the mechanical robustness and tunability of thermomechanical properties that are often characteristic of thermoset materials. These previously reported polyurethanes suffer practically because the thermoplastic molecular weights needed to achieve target cross-link densities severely limit high-throughput thermoplastic processing and because thermally unstable radiation-sensitizing additives must be used to achieve high enough cross-link densities to enable desired tunable shape memory behavior. In this study, we demonstrate the ability to manipulate cross-link density in low-molecular weight aliphatic thermoplastic polyurethane SMPs (Mw as low as ~1.5 kDa) without radiation-sensitizing additives by incorporating specific structural motifs into the thermoplastic polymer side chains that we hypothesized would significantly enhance susceptibility to e-beam cross-linking. A custom diol monomer was first synthesized and then implemented in the synthesis of neat thermoplastic polyurethane SMPs that were irradiated at doses ranging from 1 to 500 kGy. Dynamic mechanical analysis (DMA) demonstrated rubbery moduli to be tailorable between 0.1 and 55 MPa, and both DMA and sol/gel analysis results provided fundamental insight into our hypothesized mechanism of electron beam cross-linking, which enables controllable bulk cross-linking to be achieved in highly processable, low-molecular weight thermoplastic shape memory polymers without sensitizing additives. PMID

  5. Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization.

    PubMed

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

    2016-08-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust cross-linked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site-controlled propagation mechanism. Postfunctionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible cross-linked thin-film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Cross-linking of such complexes affords robust cross-linked stereocomplexes that are solvent-resistant and also exhibit considerably enhanced thermal and mechanical properties compared with the un-cross-linked stereocomplexes. PMID:27388024

  6. Cross-linked poly (vinyl alcohol)/sulfosuccinic acid polymer as an electrolyte/electrode material for H2-O2 proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Ebenezer, D.; Deshpande, Abhijit P.; Haridoss, Prathap

    2016-02-01

    Proton exchange membrane fuel cell (PEMFC) performance with a cross-linked poly (vinyl alcohol)/sulfosuccinic acid (PVA/SSA) polymer is compared with Nafion® N-115 polymer. In this study, PVA/SSA (≈5 wt. % SSA) polymer membranes are synthesized by a solution casting technique. These cross-linked PVA/SSA polymers and Nafion are used as electrolytes and ionomers in catalyst layers, to fabricate different membrane electrode assemblies (MEAs) for PEMFCs. Properties of each MEA are evaluated using scanning electron microscopy, contact angle measurements, impedance spectroscopy and hydrogen pumping technique. I-V characteristics of each cell are evaluated in a H2-O2 fuel cell testing fixture under different operating conditions. PVA/SSA ionomer causes only an additional ≈4% loss in the anode performance compared to Nafion ionomer. The maximum power density obtained from PVA/SSA based cells range from 99 to 117.4 mW cm-2 with current density range of 247 to 293.4 mA cm-2. Ionic conductivity of PVA/SSA based cells is more sensitive to state of hydration of MEA, while maximum power density obtained is less sensitive to state of hydration of MEA. Maximum power density of cross-linked PVA/SSA membrane based cell is about 35% that of Nafion® N-115 based cell. From these results, cross-linked PVA/SSA polymer is identified as potential candidate for PEMFCs.

  7. Performance of differently cross-linked, partially fluorinated proton exchange membranes in polymer electrolyte fuel cells

    SciTech Connect

    Buechi, F.N.; Gupta, B.; Haas, O.; Scherer, G.G.

    1995-09-01

    A series of differently cross-linked FEP-g-polystyrene proton exchange membranes has been synthesized by the preirradiation grafting method [FEP: poly(tetrafluoroethylene-co-hexafluoropropylene)]. Divinylbenzene (DVB) and/or triallyl cyanurate (TAC) were used as cross-linkers in the membranes. It was found that the physical properties of the membranes, such as water-uptake and specific resistance, are strongly influenced by the nature of the cross-linker. Generally it can be stated that DVB decreases water-uptake and increases specific resistance; on the other hand TAC increases swelling and decreases specific resistance to values as low as 5.0 {Omega} cm at 60 C. The membranes were tested in H{sub 2}/O{sub 2} fuel cells for stability and performance. It was found that thick (170 {micro}m) DVB cross-linked membranes showed stable operation for 1,400 h at temperatures up to 80 C. The highest power density in the fuel cell was found for the DVB and TAC double-cross-linked membrane; it exceeded the value of a cell with a Nafion{reg_sign} 117 membrane by more than 60%.

  8. Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

    SciTech Connect

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; Ren, Fei; Keum, Jong Kahk; Ahn, Suk-Kyun; Li, Dawen; Chen, Jihua

    2015-08-06

    Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition that is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.

  9. Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

    2002-01-01

    Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

  10. New paradigm for stabilization of liquid polymer films on solids

    NASA Astrophysics Data System (ADS)

    Koga, Tad; Jiang, Naisheng; Wang, Jiaxun; di, Xiaoyu; Cheung, Justin; Endoh, Maya

    2015-03-01

    We report that wetting/dewetting behavior of liquid polymer films on solids can be controlled by nanoscale architectures of polymer chains irreversibly adsorbed on the impenetrable surfaces. Monodisperse polystyrene (PS) ultrathin films (20 nm in thickness) with different molecular weights on silicon (Si) substrates with a natural amorphous Si dioxide layer were used as models. The PS thin films were annealed at high temperatures at T>Tg (Tg is the bulk glass transition temperature) for several days, and the surface structures were studied by using optical and atomic force microscopes. At the same time, the annealed PS films were further leached with a good solvent and the residue films (i.e., irreversibly adsorbed layers) were characterized by x-ray reflectivity. The experimental data reveals a strong correlation between the conformations of the adsorbed polymer chains and the stability of the liquid films on top. T. K. acknowledges the partial financial support from NSF Grant No. CMMI-1332499.

  11. 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.

  12. Compressed antisolvent precipitation and photopolymerization for the formation of crosslinked polymer microparticles useful for controlled drug delivery

    NASA Astrophysics Data System (ADS)

    Owens, Jennifer Lani

    This work presents novel antisolvent processing technique entitled Compressed Antisolvent Precipitation and Photopolymerization (CAPP) useful for forming crosslinked polymer microparticles. In this process, an organic solvent dissolves monomer and polymerization photoinitiators to form a homogeneous solution. Photopolymerization and microparticle formation occur when the homogeneous solution is sprayed into a compressed antisolvent while being simultaneously exposed to initiating light. We investigated the method of particle formation in the CAPP process to explain the repeatable bimodal particle size distribution obtained under a variety of operating conditions. Ternary phase diagrams of antisolvent, monomer, and solvent solutions were constructed and specific spray paths from the resulting ternary phase diagrams were investigated and the significance of crossing the binodal, as well as the importance of where the binodal was crossed, was discovered. In addition, manipulation of injection conditions, varying process residence times, and nucleation rate calculations were explored to further investigate the means of particle formation. We demonstrate the feasibility of encapsulating therapeutic agents into highly crosslinked polymer particles using the CAPP process. Ion-paired tacrine, erythromycin, erythromycin estolate, and erythromycin ethyl succinate were CAPP processed with poly(ethylene glycol) diacrylate monomers of several molecular weights so that the resulting particles would entrap different sized drugs in networks with varying mesh sizes. In vitro drug release profiles were obtained for all of the various drug-monomer combinations. Diffusion coefficients were estimated by fitting a short time approximation of Fickian release from a sphere of fixed diameter to the release data and were applied to a model of Fickian release from polydisperse spheres, and the results were compared to the in vitro release data. CAPP particle processing was explored in

  13. Defects in electro-optically active polymer solids

    NASA Technical Reports Server (NTRS)

    Martin, David C.

    1993-01-01

    There is considerable current interest in the application of organic and polymeric materials for electronic and photonic devices. The rapid, non-linear optical (NLO) response of these materials makes them attractive candidates for waveguides, interferometers, and frequency doublers. In order to realize the full potential of these systems, it is necessary to develop processing schemes which can fabricate these molecules into ordered arrangements. There is enormous potential for introducing well-defined, local variations in microstructure to control the photonic properties of organic materials by rational 'defect engineering.' This effort may eventually become as technologically important as the manipulation of the electronic structure of solid-state silicon based devices is at present. The success of this endeavor will require complimentary efforts in the synthesis, processing, and characterization of new materials. Detailed information about local microstructure will be necessary to understand the influence of symmetry breaking of the solid phases near point, line, and planar defects. In metallic and inorganic polycrystalline materials, defects play an important role in modifying macroscopic properties. To understand the influence of particular defects on the properties of materials, it has proven useful to isolate the defect by creating bicrystals between two-component single crystals. In this way the geometry of a grain boundary defect and its effect on macroscopic properties can be determined unambiguously. In crystalline polymers it would be valuable to establish a similar depth of understanding about the relationship between defect structure and macroscopic properties. Conventionally processed crystalline polymers have small crystallites (10-20 nm), which implies a large defect density in the solid state. Although this means that defects may play an important or even dominant role in crystalline or liquid crystalline polymer systems, it also makes it difficult

  14. Anisotropy and oxidative resistance of highly crosslinked UHMWPE after deformation processing by solid-state ram extrusion.

    PubMed

    Kurtz, Steven M; Mazzucco, Dan; Rimnac, Clare M; Schroeder, Dave

    2006-01-01

    Solid-state deformation processing is a promising technique for modifying the physical and mechanical properties of highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) beyond simple thermal treatment cycles that have been employed previously. This study evaluates anisotropy and oxidative resistance in a novel, radiation crosslinked (50 kGy) UHMWPE material (ArComXL: Biomet, Inc., Warsaw, IN), incorporating solid-state, deformation processing by extrusion below the melt transition for application in total hip arthroplasty. Tensile, compression, and small punch tests were conducted to evaluate the material properties in the three principal axes of the resulting material. Furthermore, short-term oxidative resistance was evaluated using Fourier transform infrared spectroscopy and the small punch test in conjunction with accelerated shelf aging protocols. The results of this testing indicate that the material is anisotropic, with significantly enhanced strength oriented along the long axis of the rod. For certain other properties, the magnitude of the anisotropy was relatively slight, especially in the elastic regime, in which only a 20% difference was noted between the long axis of the rod and the orthogonal, radial direction. The highly crosslinked material contains detectable free radicals, at a concentration that is 90% less than control, gamma inert sterilized UHMWPE. An unexpected finding of this study was evidence of oxidative stability of the deformation-processed material, even after 4 weeks of accelerated aging in a pressure vessel containing five atmospheres of oxygen (ASTM F2003), which resulted in macroscopic embrittlement of the control material. The oxidative stability observed in ArComXL suggests that the deformation-processed material may be suitable for air-permeable packaging and gas sterilization, which has thus far been reserved for remelted highly crosslinked UHMWPE. PMID:16085308

  15. Inexpensive cross-linked polymeric separators made from water soluble polymers

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Sheibley, D. W.

    1979-01-01

    Polyvinyl alcohol (PVA) crosslinked chemically with aldehyde reagents produces membranes which demonstrate oxidation resistance, dimensional stability, low ionic resistivity, low zincate diffusivity, and low zinc dendrite penetration rate which make them suitable for use as alkaline battery separators. They are intrinsically low in cost and environmental health and safety problems associated with commercial production appear minimal. Preparation, property measurements, and cell test results in Ni/Zn and Ag/Zn cells are described and discussed.

  16. Oxidation increases mucin polymer cross-links to stiffen airway mucus gels

    PubMed Central

    Yuan, Shaopeng; Hollinger, Martin; Lachowicz-Scroggins, Marrah E.; Kerr, Sheena C.; Dunican, Eleanor M.; Daniel, Brian M.; Ghosh, Sudakshina; Erzurum, Serpel C.; Willard, Belinda; Hazen, Stanley L.; Huang, Xiaozhu; Carrington, Stephen D.; Oscarson, Stefan; Fahy, John V.

    2015-01-01

    Airway mucus in cystic fibrosis (CF) is highly elastic, but the mechanism behind this pathology is unclear. We hypothesized that the biophysical properties of CF mucus are altered because of neutrophilic oxidative stress. Using confocal imaging, rheology, and biochemical measures of inflammation and oxidation, we found that CF airway mucus gels have a molecular architecture characterized by a core of mucin covered by a web of DNA and a rheological profile characterized by high elasticity that can be normalized by chemical reduction. We also found that high levels of reactive oxygen species in CF mucus correlated positively and significantly with high concentrations of the oxidized products of cysteine (disulfide cross-links). To directly determine whether oxidation can cross-link mucins to increase mucus elasticity, we exposed induced sputum from healthy subjects to oxidizing stimuli and found a marked and thiol-dependent increase in sputum elasticity. Targeting mucin disulfide cross-links using current thiol-amino structures such as N-acetylcysteine (NAC) requires high drug concentrations to have mucolytic effects. We therefore synthesized a thiol-carbohydrate structure (methyl 6-thio-6-deoxy-α-D-galactopyranoside) and found that it had stronger reducing activity than NAC and more potent and fast-acting mucolytic activity in CF sputum. Thus, oxidation arising from airway inflammation or environmental exposure contributes to pathologic mucus gel formation in the lung, which suggests that it can be targeted by thiol-modified carbohydrates. PMID:25717100

  17. Oxidation increases mucin polymer cross-links to stiffen airway mucus gels.

    PubMed

    Yuan, Shaopeng; Hollinger, Martin; Lachowicz-Scroggins, Marrah E; Kerr, Sheena C; Dunican, Eleanor M; Daniel, Brian M; Ghosh, Sudakshina; Erzurum, Serpel C; Willard, Belinda; Hazen, Stanley L; Huang, Xiaozhu; Carrington, Stephen D; Oscarson, Stefan; Fahy, John V

    2015-02-25

    Airway mucus in cystic fibrosis (CF) is highly elastic, but the mechanism behind this pathology is unclear. We hypothesized that the biophysical properties of CF mucus are altered because of neutrophilic oxidative stress. Using confocal imaging, rheology, and biochemical measures of inflammation and oxidation, we found that CF airway mucus gels have a molecular architecture characterized by a core of mucin covered by a web of DNA and a rheological profile characterized by high elasticity that can be normalized by chemical reduction. We also found that high levels of reactive oxygen species in CF mucus correlated positively and significantly with high concentrations of the oxidized products of cysteine (disulfide cross-links). To directly determine whether oxidation can cross-link mucins to increase mucus elasticity, we exposed induced sputum from healthy subjects to oxidizing stimuli and found a marked and thiol-dependent increase in sputum elasticity. Targeting mucin disulfide cross-links using current thiol-amino structures such as N-acetylcysteine (NAC) requires high drug concentrations to have mucolytic effects. We therefore synthesized a thiol-carbohydrate structure (methyl 6-thio-6-deoxy-α-D-galactopyranoside) and found that it had stronger reducing activity than NAC and more potent and fast-acting mucolytic activity in CF sputum. Thus, oxidation arising from airway inflammation or environmental exposure contributes to pathologic mucus gel formation in the lung, which suggests that it can be targeted by thiol-modified carbohydrates. PMID:25717100

  18. Architectures for controlling solid state properties of conjugated polymers

    NASA Astrophysics Data System (ADS)

    Nambiar, Rakesh R.

    Conjugated polymers and oligomers are great materials for use in the next generation devices namely organic field effect transistors, light emitting diodes and polymeric solar cells. Apart from having the potential for developing power-efficient, flexible, robust and inexpensive devices, conjugated polymers can also be tuned by molecular design to optimize device characteristics. One key problem for the full commercial exploitation of conjugated polymers is that the charge carrier mobility of the state-of-the-art polymer semiconductors is much lower than required for many applications. The performance of the devices is strongly dependent on the molecular structure and supermolecular assembly of the conjugated polymer chains. This thesis covers our attempts to design molecular structure to control and improve the solid state properties of conjugated polymers. The relative placement of side chains along the backbone has a great influence on the solid state ordering of conjugated polymers. Poly(2,5-disubstituted-1,4-phenylene ethynylene)s (PPE)s, an important class of conjugated polymers, are generally synthesized by Pd-catalyzed coupling polymerizations of appropriately substituted diiodo and diethynyl benzenes (i.e., A-A and B-B type monomers). In asymmetrically substituted PPEs, this results in an irregular substitution pattern of the side chains along the polymer backbone. We report a new synthetic approach to prepare regioregular unsymmetrically substituted PPEs by polymerization of 4-iodophenylacetylenes (i.e., A-B type monomer). We provide a detailed discussion of various approaches to the synthesis of PPEs with different regioregularities and provide a description of the differences between regioregular and regiorandom analogs. The effect of regioregularity becomes even more important when the two side chains are very dissimilar or amphiphilic. We explore the effect of relative placement hydrophobic (dodecyloxy)/hydrophilic (tri(ethylene glycol) and

  19. Enhancement in dose sensitivity of polymer gel dosimeters composed of radiation-crosslinked gel matrix and less toxic monomers

    NASA Astrophysics Data System (ADS)

    Hiroki, A.; Yamashita, S.; Taguchi, M.

    2015-01-01

    Polymer gel dosimeters based on radiation-crosslinked hydroxypropyl cellulose gel were prepared, which comprised 2-hydroxyethyl methacrylate (HEMA) and polyethylene glycol #400 dimethacrylate (9G) as less toxic monomers and tetrakis (hydroxymethyl) phosphonium chloride (THPC) as an antioxidant. The dosimeters exposed to 60Co γ-rays became cloudy at only 1 Gy. The irradiated dosimeters were optically analyzed by using a UV- vis spectrophotometer to evaluate dose response. Absorbance of the dosimeters linearly increased in the dose range from 0 to 10 Gy, in which dose sensitivity increased with increasing 9G concentration. The dose sensitivity of the dosimeters with 2 wt% HEMA and 3 wt% 9G was also enhanced by increment in THPC.

  20. 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

  1. Study of Hydrophobic and Ionizable Hydrophilic Copolymers at Polymer/Solid and Polymer/Liquid Interfaces

    SciTech Connect

    Perahia, Dvora

    2011-11-01

    Joint experimental-computational efforts were set to characterize the interfacial effects on the structure and dynamics of polymers consisting of highly rigid hydrophilic-ionizable and hydrophobic sub-units within one polymeric chain casted into thin films of several molecular dimensions. Focusing on the ultra thin film region we separate out the interfacial effects from bulk characteristics. Specifically, the study sought to: identify the parameters that control the formation of a stable polymer-solid interface. The study consists of two components, experimental investigations and computational efforts. The experimental component was designed to derive empirical trends that can be used to correlate the set of coupled polymer molecular parameters with the interfacial characteristics of these polymers, and their response to presence of solvents. The computational study was designed to provide molecular insight into the ensemble averages provided by the experimental efforts on multiple length scales from molecular dimensions, to the nanometer lengths to a macroscopic understanding of solvent interactions with structured polymers. With the ultimate goal of correlating molecular parameters to structure, dynamics and properties of ionic polymers, the first stage of the research began with the study of two systems, one which allowed tailoring the flexibility of the backbone without the presence of ionic groups, but with a potential to sulfonate groups at a later stage, and a polymer whose backbone is rigid and the density of the ionic group can be varied. The combined experimental and computational studies significantly extended the understanding of polymers at interfaces from model systems to polydispersed copolymers with blocks of varying nature and complexity. This new insight directly affects the design of polymers for sustainable energy applications from batteries and fuel cells to solar energy.

  2. Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

    SciTech Connect

    Liao, Chen; Sun, Xiao-Guang; Dai, Sheng

    2013-01-01

    Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

  3. Bioreducible cross-linked polymers based on G1 peptide dendrimer as potential gene delivery vectors.

    PubMed

    Li, Chun-Yan; Wang, Hai-Jiao; Cao, Jing-Ming; Zhang, Ji; Yu, Xiao-Qi

    2014-11-24

    A series of cationic polymers based on low generation (G1) peptide dendrimer were synthesized with disulfide-containing linkages. The DNA binding abilities of the target polymers were studied by gel electrophoresis and fluorescence quenching assay. The bioreducible property of the disulfide-containing polymers P2 and P3 was also investigated in the presence of dithiothreitol (DTT). Results from dynamic light scattering (DLS) and transmission electron microscopy (TEM) assays reveal that these materials may condense DNA into nanoparticles with proper sizes and zeta-potentials. In vitro cell experiments show that compared to branched 25 KDa PEI, P2 and P3 may exhibit much higher gene transfection efficiency and lower cytotoxicity in both HEK293 and U-2OS cells. Additionally, polymer prepared from Michael addition gives better gene transfection ability, while polymer prepared from ring-opening reaction has better serum tolerance. Results indicate that these polymers might be promising non-viral gene vectors for their easy preparation, very low cytotoxicity, and good transfection efficiency. PMID:25282264

  4. Highly efficient and stable inverted polymer solar cells integrated with a cross-linked fullerene material as an interlayer.

    PubMed

    Hsieh, Chao-Hsiang; Cheng, Yen-Ju; Li, Pei-Jung; Chen, Chiu-Hsiang; Dubosc, Martin; Liang, Ru-Meng; Hsu, Chain-Shu

    2010-04-01

    A novel PCBM-based n-type material, [6,6]-phenyl-C(61)-butyric styryl dendron ester (PCBSD), functionalized with a dendron containing two styryl groups as thermal cross-linkers, has been rationally designed and easily synthesized. In situ cross-linking of PCBSD was carried out by heating at a low temperature of 160 degrees C for 30 min to generate a robust, adhesive, and solvent-resistant thin film. This cross-linked network enables a sequential active layer to be successfully deposited on top of this interlayer to overcome the problem of interfacial erosion and realize a multilayer inverted device by all-solution processing. An inverted solar cell device based on an ITO/ZnO/C-PCBSD/P3HT:PCBM/PEDOT:PSS/Ag configuration not only achieves enhanced device characteristics, with an impressive PCE of 4.4%, but also exhibits an exceptional device lifetime without encapsulation; it greatly outperforms a reference device (PCE = 3.5%) based on an ITO/ZnO/P3HT:PCBM/PEDOT:PSS/Ag configuration without the interlayer. This C-PCBSD interlayer exerts multiple positive effects on both P3HT/C-PCBSD and PCBM/C-PCBSD localized heterojunctions at the interface of the active layer, including improved exciton dissociation efficiency, reduced charge recombination, decreased interface contact resistance, and induction of vertical phase separation to reduce the bulk resistance of the active layer as well as passivation of the local shunts at the ZnO interface. Moreover, this promising approach can be applied to another inverted solar cell, ITO/ZnO/C-PCBSD/PCPDTBT:PC(71)BM/PEDOT:PSS/Ag, using PCPDTBT as the p-type low-band-gap conjugated polymer to achieve an improved PCE of 3.4%. Incorporation of this cross-linked C(60) interlayer could become a standard procedure in the fabrication of highly efficient and stable multilayer inverted solar cells. PMID:20222734

  5. Folic acid conjugated cross-linked acrylic polymer (FA-CLAP) hydrogel for site specific delivery of hydrophobic drugs to cancer cells

    PubMed Central

    2014-01-01

    Background The hydrogel based system is found to be rarely reported for the delivery of hydrophobic drug due to the incompatibility of hydrophilicity of the polymer network and the hydrophobicity of drug. This problem can be solved by preparing semi-interpenetrating network of cross-linked polymer for tuning the hydrophilicity so as to entrap the hydrophobic drugs. The current study is to develop a folic acid conjugated cross-linked pH sensitive, biocompatible polymeric hydrogel to achieve a site specific drug delivery. For that, we have synthesized a folic acid conjugated PEG cross-linked acrylic polymer (FA-CLAP) hydrogel and investigated its loading and release of curcumin. The formed polymer hydrogel was then conjugated with folic acid for the site specific delivery of curcumin to cancer cells and then further characterized and conducted the cell uptake and cytotoxicity studies on human cervical cancer cell lines (HeLa). Results In this study, we synthesized folic acid conjugated cross-linked acrylic hydrogel for the delivery of hydrophobic drugs to the cancer site. Poly (ethyleneglycol) (PEG) diacrylate cross-linked acrylic polymer (PAA) was prepared via inverse emulsion polymerization technique and later conjugated it with folic acid (FA-CLAP). Hydrophobic drug curcumin is entrapped into it and investigated the entrapment efficiency. Characterization of synthesized hydogel was done by using Fourier Transform-Infrared spectroscopy (FT-IR), Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC). Polymerization and folate conjugation was confirmed by FT-IR spectroscopy. The release kinetics of drug from the entrapped form was studied which showed initial burst release followed by sustained release due to swelling and increased cross-linking. In vitro cytotoxicity and cell uptake studies were conducted in human cervical cancer (HeLa) cell lines. Conclusions Results showed that curcumin entrapped folate conjugated cross-linked acrylic

  6. Adhesive force assisted imprinting of soft solid polymer films by flexible foils.

    PubMed

    Mukherjee, Rabibrata; Sharma, Ashutosh; Gonuguntla, Manoj; Patil, Ganesh K

    2008-07-01

    We report a simple, rapid, room temperature, pressure-less and large area (approximately cm2) imprinting technique for high fidelity patterning of soft solid polymer films and surfaces like cross-linked polydimethylsiloxane (PDMS) and polyacrylamide (PAA) based hydrogels, both on planar and curved surfaces. The key element of the method is the use of patterned thin flexible foils that readily and rapidly attain a conformal contact with soft (shear modulus < 0.1 MPa) solid surfaces because of adhesive interfacial interactions. The conformal contact is established at all length scales by bending of the foil at scales larger than the feature size, in conjunction with the spontaneous elastic deformations of the surface on the scale of the features. For example, we used the protective aluminum foils of commercial data storage discs, both with or without data stored, for micron and sub-micron pattern transfer. The patterns are made permanent by UV-ozone treatment (for PDMS) or by controlled drying (for hydrogels). Interestingly, elastic contact imprinting of very thin (< 300 nm) films results in about 50% miniaturization of the original foil feature sizes. Complex two dimensional patterns could also be formed even by using a simple one dimensional master by multiple imprinting. The technique can be particularly useful for the bulk nano applications requiring routine fabrication of templates, for example, in the study of confined chemistry phenomena, nanofluidics, bio-MEMS, micro-imprinting, optical coatings and controlled dewetting. PMID:19051887

  7. Wet air oxidation of solid waste made of polymers

    SciTech Connect

    Krisner, E.; Ambrosio, M.; Massiani, C.

    2000-03-01

    Wet air oxidation was attempted on synthetic (mixture of plastics of various compositions) and natural (cellulose substances) solid polymers. The temperature was maintained at 270 C and the oxygen pressure varied from 0 to 2 MPa (from understoichiometric conditions to oxygen excess). No valorizable compounds were found, even in runs carried out under an oxygen deficit. Suitable conditions for the total destruction of the initial polymers were temperatures above 270 C, an excess of oxygen, and a residence time of less than 1 h. Only such degradable compounds as acetic and benzoic acids are found at low concentrations. Formation of chlorine and gaseous hydrochloric acid can be limited by adding CaCO{sub 3} as a neutralizing agent.

  8. Robust solid polymer electrolyte for conducting IPN actuators

    NASA Astrophysics Data System (ADS)

    Festin, Nicolas; Maziz, Ali; Plesse, Cédric; Teyssié, Dominique; Chevrot, Claude; Vidal, Frédéric

    2013-10-01

    Interpenetrating polymer networks (IPNs) based on nitrile butadiene rubber (NBR) as first component and poly(ethylene oxide) (PEO) as second component were synthesized and used as a solid polymer electrolyte film in the design of a mechanically robust conducting IPN actuator. IPN mechanical properties and morphologies were mainly investigated by dynamic mechanical analysis and transmission electron microscopy. For 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide (EMITFSI) swollen IPNs, conductivity values are close to 1 × 10-3 S cm-1 at 25 ° C. Conducting IPN actuators have been synthesized by chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) within the PEO/NBR IPN. A pseudo-trilayer configuration has been obtained with PEO/NBR IPN sandwiched between two interpenetrated PEDOT electrodes. The robust conducting IPN actuators showed a free strain of 2.4% and a blocking force of 30 mN for a low applied potential of ±2 V.

  9. Solid hemoglobin-polymer phantoms for evaluation of biophotonic systems.

    PubMed

    Jang, Hyounguk; Pfefer, T Joshua; Chen, Yu

    2015-09-15

    Stable tissue phantoms that incorporate the spectral absorption properties of hemoglobin would benefit a wide range of biophotonic technologies. Toward this end, we have developed and validated a novel polymer material incorporating hemoglobin. Our solid hemoglobin-polymer (SHP) material is fabricated by mixing liquid silicone base with a hemoglobin solution, followed by sonication and low temperature curing. The optical properties of samples were determined over 450-1000 nm using the inverse adding-doubling method and the Beer-Lambert law. Measurements indicated SHP optical stability over four months. Near-infrared spectroscopy and hyperspectral imaging measurements of SHP samples were performed to demonstrate the utility of this approach. SHP materials have the potential to improve tissue-simulating phantoms used for development, evaluation, and standardization of optical devices for oximetry and other applications. PMID:26371926

  10. Fuel cells with solid polymer electrolyte and their application on vehicles

    SciTech Connect

    Fateev, V.

    1996-04-01

    In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

  11. Characterization of particle morphology of biochanin A molecularly imprinted polymers and their properties as a potential sorbent for solid-phase extraction.

    PubMed

    Chrzanowska, Anna M; Poliwoda, Anna; Wieczorek, Piotr P

    2015-04-01

    Molecularly imprinted polymers (MIPs) with biochanin A as a template were obtained using a bulk polymerization with non-covalent imprinting approach. The polymers were prepared in acetonitrile as porogen, using ethylene glycol dimethacrylate (EDMA) as cross-linking agent. The synthesis, with an application of 1',1'-azobis(cyclohexanecarbonitrile) (ACHN) as an initiator, has been performed thermally. During the synthesis process the effect of different functional monomers such as methacrylic acid (MAA), acrylamide (AA) and 4-vinylpyridine (4-VP) was investigated. The application of nitrogen sorption porosimetry, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) permitted the characterization and evaluation of synthesized polymers. The adsorption capacity of obtained MIPs was checked by using the binding testing. All synthesized polymers were evaluated as solid-phase extraction (SPE) sorbents for isolation and preconcentration of biochanin A and its analogues, daidzein and genistein. The MIPs exhibited higher affinity for biochanin A over competitive compounds. PMID:25687010

  12. High-Voltage Solid Polymer Batteries for Electric Drive Vehicles

    SciTech Connect

    Eitouni, Hany; Yang, Jin; Pratt, Russell; Wang, Xiao; Grape, Ulrik

    2014-09-29

    The purpose of this project was for Seeo to develop a high energy lithium based technology with targets of over 500 Wh/l and 325 Wh/kg. Seeo would leverage the work already achieved with its unique proprietary solid polymer DryLyteTM technology in cells which had a specific energy density of 220 Wh/kg. The development work was focused on establishing a dual electrolyte system, coated cathode particle techniques, various types of additives, and different conductive salts. The program had a duration of three years, with Seeo delivering the final cells at the end of 2014 for evaluation by a DOE laboratory.

  13. Recent advances in solid polymer electrolyte fuel cell technology

    SciTech Connect

    Ticianelli, E.A.; Srinivasan, S.; Gonzalez, E.R.

    1988-01-01

    With methods used to advance solid polymer electrolyte fuel cell technology, we are close to obtaining the goal of 1 A/cm/sup 2/ at 0.7. Higher power densities have been reported (2 A/cm/sup 2/ at 0.5 V) but only with high catalyst loading electrodes (2 mg/cm/sup 2/ and 4 mg/cm/sup 2/ at anode and cathode, respectively) and using a Dow membrane with a better conductivity and water retention characteristics. Work is in progress to ascertain performances of cells with Dow membrane impregnated electrodes and Dow membrane electrolytes. 5 refs., 6 figs.

  14. Electrolytic hydrogen fuel production with solid polymer electrolyte technology.

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Fickett, A. P.

    1973-01-01

    A water electrolysis technology based on a solid polymer electrolyte (SPE) concept is presented for applicability to large-scale hydrogen production in a future energy system. High cell current density operation is selected for the application, and supporting cell test performance data are presented. Demonstrated cell life data are included to support the adaptability of the SPE system to large-size hydrogen generation utility plants as needed for bulk energy storage or transmission. The inherent system advantages of the acid SPE electrolysis technology are explained. System performance predictions are made through the year 2000, along with plant capital and operating cost projections.

  15. Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy.

    PubMed

    Janko, Marek; Jocher, Michael; Boehm, Alexander; Babel, Laura; Bump, Steven; Biesalski, Markus; Meckel, Tobias; Stark, Robert W

    2015-07-13

    The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper. PMID:26101966

  16. Effect of Network Structure/Topology on Mechanical Properties of Crosslinked Polymers

    NASA Astrophysics Data System (ADS)

    Sharifi, Majid

    The interest in epoxy thermosetting polymers is widespread (e.g. Boeing 787 Dreamliner, windmill blades, automobiles, coatings, adhesives, etc.), and a demand still exists for improving toughness of these materials without degrading advantageous properties such as strength, modulus, and Tg. This study introduces novel approaches for improving the intrinsic mechanical characteristics of these polymers. The designed synthetic techniques focus on developing polymer materials with the same overall compositions but varying in network topologies, with distinct topological features in the size range of 5-50 nm, measured by SAXS and SEM. It was found that without altering chemical structure, the network topology of a dense thermoset can be engineered such that, under mechanical deformation, nano-cavities open and dissipate energy before rupturing covalent bonds, producing a tougher material without sacrificing strength, modulus, and even glass transition temperature. Modified structures also revealed higher resistance to fracture than the corresponding control structures. The major fracture mechanism responsible for the increased energy dissipation was found to be nano-cavitation. SEM images from the fracture surfaces showed clear cavities on the modified samples whereas none were seen on the fracture surface of the control samples. Overall, it was demonstrated that network topology can be used to tailor thermal and mechanical properties of thermosetting polymers. The experimental methodologies in this dissertation can directly and economically be applied to design polymeric materials with improved properties for desired applications. Although topology-based toughening was investigated on epoxy-amine polymers, the concept can be extended to most thermoset chemistries and perhaps to other brittle network forming materials.

  17. Molecularly imprinted polymer grafted to porous polyethylene frits: a new selective solid-phase extraction format.

    PubMed

    Barahona, Francisco; Turiel, Esther; Martín-Esteban, Antonio

    2011-10-01

    In this paper, a novel format for selective solid-phase extraction based on a molecularly imprinted polymer (MIP) is described. A small amount of MIP has been synthesized within the pores of commercial polyethylene (PE) frits and attached to its surface using benzophenone (BP), a photo-initiator capable to start the polymerisation from the surface of the support material. Key properties affecting the obtainment of a proper polymeric layer, such as polymerisation time and kind of cross-linker were optimised. The developed imprinted material has been applied as a selective sorbent for cleaning extracts of thiabendazole (TBZ), as model compound, from citrus samples. The use of different solvents for loading the analyte in the imprinted frits was investigated, as well as the binding capacity of the imprinted polymer. Imprinted frits showed good selectivity when loads were performed using toluene and a linear relationship was obtained for the target analyte up to 1000 ng of loaded analyte. Prepared composite material was applied to the SPE of TBZ in real samples extracts, showing an impressive clean-up ability. Calibrations showed good linearity in the concentration range of 0.05-5.00 μg g(-1), referred to the original solid sample, and the regression coefficients obtained were greater than 0.996. The calculated detection limit was 0.016 μg g(-1), low enough to satisfactory analysis of TBZ in real samples. RSDs at different spiking levels ranged below 15% in all the cases and imprinted frits were reusable without loss in their performance. PMID:21855075

  18. Stationary market applications potential of solid oxide and solid polymer fuel cell systems

    SciTech Connect

    Baker, J.N.; Fletcher, W.H.

    1996-12-31

    The UK DTI`s Advanced Fuel Cells Programme currently focuses on two main fuel cell technologies, namely the solid oxide and solid polymer systems (SOFC and SPFC), respectively. The provision of accurate and timely market data is regarded as an important part of the overall programme objectives, such as to assist both Government and industry in their appraisals of the technologies. The present study was therefore commissioned against this background, with a complementary study addressing transportation and mobile applications. The results reported herein relate to the stationary market applications potential of both SOFC and SPFC systems.

  19. MeV ion beam interaction with polymer films containing cross-linking agents

    SciTech Connect

    Evelyn, A. L.

    1999-06-10

    Polymer films containing cross linking enhancers were irradiated with MeV alpha particles to determine the effects of MeV ion beam interaction on these materials. The contributed effects from the electronic and nuclear stopping powers were separated by irradiating stacked thin films of polyvinyl chloride (PVC), polystyrene (PS) and polyethersulfone (PES). This layered system allowed most of the effects of the electronic energy deposited to be experienced by the first layers and the last layers to receive most of the effects of the nuclear stopping power. RGA, Raman microprobe analysis, RBS and FTIR measured changes in the chemical structures of the irradiated films. The characterization resolved the effects of the stopping powers on the PVC, PS and PES and the results were compared with those from previously studied polymers that did not contain any cross linking agents.

  20. Dynamic Bonds in Covalently Crosslinked Polymer Networks for Photoactivated Strengthening and Healing.

    PubMed

    Gordon, Melissa B; French, Jonathan M; Wagner, Norman J; Kloxin, Christopher J

    2015-12-22

    A photoactivated-strengthening polymer network is reported. This approach incorporates dynamic bonds into the network architecture, which enables a secondary polymerization triggered by UV light. Three attributes of this material are demonstrated, including: i) there is simultaneous photoinduced strengthening and healing after the material is severed, ii) bulk property changes are spatially confined via photopatterning, and iii) there is permanent shape change post-irradiation. PMID:26524195

  1. Retention of aroma compounds from Mentha piperita essential oil by cyclodextrins and crosslinked cyclodextrin polymers.

    PubMed

    Ciobanu, A; Mallard, I; Landy, D; Brabie, G; Nistor, D; Fourmentin, S

    2013-05-01

    In this paper, the controlled release of aroma compounds from cyclodextrins (CDs) and CD polymers was studied by multiple headspace extraction (MHE) experiments. Mentha piperita essential oil was obtained by Soxhlet extraction and identification of the major compounds was performed by GC-MS analysis. Menthol, menthone, pulegone and eucalyptol were identified as the major components. Retention of standard compounds in the presence of different CDs and CD polymers has been realised by static headspace gas chromatography (SH-GC) at 25 °C in the aqueous or gaseous phase. Stability constants for standard compounds and for compounds in essential oil have been also determined with monomeric CD derivatives. The obtained results indicated the formation of a 1:1 inclusion complex for all the studied compounds. Molecular modelling was used to investigate the complementarities between host and guest. This study showed that β-CDs were the most versatile CDs and that β-CD polymers could perform the controlled release of aroma compounds. PMID:23265490

  2. The Effect of Filler-Polymer Interactions on Cold-Crystallization Kinetics in Crosslinked, Silica Filled PDMS/PDPS Copolymer Melts.

    SciTech Connect

    Chien, A; DeTeresa, S; Thompson, L; Cohenour, R; Balazs, B; Maxwell, R S

    2006-04-21

    Crystallization in a series of variable crosslink density poly(dimethyl-diphenyl) siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and X-ray Diffraction (XRD). The silicone composite studied was composed of 94.6 mol% Dimethoylsiloxane, 5.1 mol% diphenylsiloxane, and 0.3 mol% methyl-vinyl siloxane (which formed crosslinking after a peroxide cure). The polymer was filled with a mixture of 21.6 wt. % fumed silica and 4.0 wt. % precipitated silica previously treated with 6.8 wt. % ethoxy-endblocked siloxane processing aid. The base composite was characterized by a molecular weight between crosslinks in the polymer network of {approx}24 kDa and an overall molecular weight (including the influence of the silica fillers) between crosslinks of {approx}11 kDa. Molecular weight between crosslinks and filler-polymer interaction strength were then modified by exposure to {gamma}-irradiation in either air or vacuum. The unirradiated material exhibited crystallization at -80 C as measured by DSC with a 16% crystallization as measured by XRD. Isothermal DMA experiments illustrated that crystallization at -85 C occurred over a 1.8 hour period in silica-filled systems and 2.2-2.6 hours in unfilled systems. The onset of crystallization typically occurred after a 30-minute incubation/nucleation period. The crystallization kinetics were dependent on crosslink density. Changes in molecular weight of a factor of two did not, however, change the amount of crystallization. Irradiation in vacuum resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface. Modulated differential scanning calorimetry contrasted the crystallization and melting behavior of pure PDMS versus the PDMS/PDPS base

  3. Organic crosslinking of polymers for CO/sub 2/ flooding profile control

    SciTech Connect

    Mitchell, T.O.

    1988-12-27

    A method is described for recovering hydrocarbonaceous fluids from a formation having a substantially low pH, penetrated by at least one injection well and fluidly communicating with at least one production well which formation contains a low permeability and a high permeability zone comprising: (a) mixing together above ground, water, a biopolymer selected from the group consisting of Xanthan polysacharides, Alcalignee polysaccharides, and mixtures thereof in an amount of about 0.2 to about 5.0 weight percent; (b) maintaining the mixture at a Ph of less than about 5.5; (c) adding only sufficient aminoplast resin as a crosslinker to form a rehealable gel which forms in about 0.5 to about 6.0 hours at ambient temperature and which is of a size sufficient to selectively close pores in the high permeability zone; (d) injecting via the injection well into the high permeability zone the gel in an amount sufficient to selectively close pores in the high permeability zone; (e) injecting via the injection well into the low permeability zone a drive fluid in an amount sufficient to remove hydrocarbonaceous fluids from low permeability zone which fluid is diverted from high permeability zone containing the closed pores and (f) recovering hydrocarbonaceous fluids and the drive fluid from the low permeability zone via the production well.

  4. Feasibility of Crosslinked Acrylic Shape Memory Polymer for a Thrombectomy Device

    PubMed Central

    Muschenborn, Andrea D.; Hearon, Keith; Volk, Brent L.; Conway, Jordan W.; Maitland, Duncan J.

    2014-01-01

    Purpose To evaluate the feasibility of utilizing a system of SMP acrylates for a thrombectomy device by determining an optimal crosslink density that provides both adequate recovery stress for blood clot removal and sufficient strain capacity to enable catheter delivery. Methods Four thermoset acrylic copolymers containing benzylmethacrylate (BzMA) and bisphenol A ethoxylate diacrylate (Mn~512, BPA) were designed with differing thermomechanical properties. Finite element analysis (FEA) was performed to ensure that the materials were able to undergo the strains imposed by crimping, and fabricated devices were subjected to force-monitored crimping, constrained recovery, and bench-top thrombectomy. Results Devices with 25 and 35 mole% BPA exhibited the highest recovery stress and the highest brittle response as they broke upon constrained recovery. On the contrary, the 15 mole % BPA devices endured all testing and their recovery stress (5 kPa) enabled successful bench-top thrombectomy in 2/3 times, compared to 0/3 for the devices with the lowest BPA content. Conclusion While the 15 mole% BPA devices provided the best trade-off between device integrity and performance, other SMP systems that offer recovery stresses above 5 kPa without increasing brittleness to the point of causing device failure would be more suitable for this application. PMID:25414549

  5. Does filler surface chemistry impact filler dispersion, polymer dynamics and conductivity in nanofilled solid polymer electrolytes?

    NASA Astrophysics Data System (ADS)

    Ganapatibhotla, Lalitha; Maranas, Janna

    2012-02-01

    We study the impact of nanofiller surface chemistry on filler dispersion, polymer dynamics and ionic conductivity in acidic α-Al2O3 filled PEO+LiClO4 solid polymer electrolytes (SPEs).SPEs are the key to light-weight and high energy density rechargeable Li ion batteries but suffer from low room temperature ionic conductivity. Addition of ceramic nanofillers improves conductivity of SPEs and their surface chemistry influences extent of conductivity enhancement. The ionic conductivity of acidic α-Al2O3 filled SPE is enhanced for salt concentrations at and below eutectic, while neutral γ-Al2O3 filler enhances conductivity only at eutectic composition. Li ion motion is coupled to segmental mobility of polymer and we study how this is affected by addition of α-Al2O3 using quasi-elastic neutron scattering. Aggregation extent of nanoparticles in SPE matrix, a less explored factor in filled SPEs, can affect segmental mobility of polymer. This can vary with surface chemistry of particles and we quantify this using small angle neutron scattering. All measurements are performed as a function of Li concentration, nanoparticle loading and temperature.

  6. Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

    2015-03-01

    Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

  7. Equilibrium chain conformations of bound polymers at the polymer melt/solid interface

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Sendogdular, Levent; Endoh, Maya; Koga, Tadanori

    2014-03-01

    We report the equilibrium conformations of bound polymer chains formed on planar solids. In this study, bound polystyrene (PS) layers onto silicon (Si) substrates were used as a model system. Three 50 nm-thick PS thin films were prepared by using different film processes (i.e., spin coating, dip coating, and floating) following prolonged thermal annealing and subsequent solvent leaching. The structures of the bound layers on Si were then characterized by using x-ray reflectivity and atomic force microscopy. We found that the adsorption kinetics for the dip coating film is much longer than that for the spun cast film or the floating film. It was also found that all the bound PS layers are composed of two different nanoarchitectures: flattened chains that constitute the inner higher density region of the bound layers and loosely adsorbed polymer chains that form the outer bulk-like density region. We acknowledge the financial support from NSF Grant No. CMMI-084626.

  8. 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.

  9. Influences of dehydration and rehydration on the lubrication properties of phospholipid polymer-grafted cross-linked polyethylene.

    PubMed

    Yarimitsu, Seido; Moro, Toru; Kyomoto, Masayuki; Watanabe, Kenichi; Tanaka, Sakae; Ishihara, Kazuhiko; Murakami, Teruo

    2015-07-01

    Surface modification by grafting of biocompatible phospholipid polymer onto the surface of artificial joint material has been proposed to reduce the risk of aseptic loosening and improve the durability. Poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-grafted cross-linked polyethylene (CLPE) has shown promising results for reducing wear of CLPE. The main lubrication mechanism for the PMPC layer is considered to be the hydration lubrication. In this study, the lubrication properties of PMPC-grafted CLPE were evaluated in reciprocating friction test with rehydration process by unloading in various lubricants. The start-up friction of PMPC-grafted CLPE was reduced, and the damage of PMPC layer was suppressed by rehydration in water or hyaluronic acid solutions. In contrast, the start-up friction of PMPC-grafted CLPE increased in fetal bovine serum solution, and the damage for PMPC layer was quite noticeable. Interestingly, the start-up friction of PMPC-grafted CLPE was reduced in fetal bovine serum solution containing hyaluronic acid, and the damage of the PMPC layer was suppressed. These results indicate that the rehydration by unloading and hyaluronic acid are elemental in maximizing the lubrication effect of hydrated PMPC layer. PMID:26036469

  10. Dually actuated triple shape memory polymers of cross-linked polycyclooctene-carbon nanotube/polyethylene nanocomposites.

    PubMed

    Wang, Zhenwen; Zhao, Jun; Chen, Min; Yang, Minhao; Tang, Luyang; Dang, Zhi-Min; Chen, Fenghua; Huang, Miaoming; Dong, Xia

    2014-11-26

    In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices. PMID:25347728

  11. 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

  12. Methylene crosslinked calix[6]arene hexacaarboxylic acid resin: a highly efficient solid phase extractant for decontamination of lead bearing effluents.

    PubMed

    Adhikari, Birendra Babu; Gurung, Manju; Kawakita, Hidetaka; Jumina; Ohto, Keisuke

    2011-10-15

    Calixarene-based cation exchange resin has been developed by methylene crosslinking of calix[6]arene hexacarboxylic acid derivative and the resin has been exploited for solid phase extraction of some toxic heavy metal ions. The selectivity order of the resin towards some metal ions follows the order Pb(II) > Cu(II)> Zn(II), Ni(II), Co(II). The maximum lead ion binding capacity of the resin was found to be 1.30 mmol g(-1) resin. The loaded lead was quantitatively eluted with dilute acid solution regenerating the resin. Mutual separation of Pb(II), Cu(II) and Zn(II) was achieved by using the column packed with the resin. PMID:21835544

  13. Hemostatic potential of natural/synthetic polymer based hydrogels crosslinked by gamma radiation

    NASA Astrophysics Data System (ADS)

    Barba, Bin Jeremiah D.; Tranquilan-Aranilla, Charito; Abad, Lucille V.

    2016-01-01

    Various raw materials and hydrogels prepared from their combination were assessed for hemostatic capability using swine whole blood clotting analysis. Initial screening showed efficient coagulative properties from κ-carrageenan and its carboxymethylated form, and α-chitosan, even compared to commercial products like QuikClot Zeolite Powder. Blending natural and synthetic polymers formed into hydrogels using gamma radiation produced materials with improved properties. KC and CMKC hydrogels were found to have the lowest blood clotting index in granulated form and had the higher capacity for platelet adhesion in foamed form compared to GelFoam. Possible mechanisms involved in the evident thrombogenicity of the materials include adsorption of platelets and related proteins that aid in platelet activation (primary hemostasis), absorption of water to concentrate protein factors that control the coagulation cascade, contact activation by its negatively charged surface and the formation of gel-blood clots.

  14. A triarylboron-based fluorescent temperature indicator: sensitive both in solid polymers and in liquid solvents.

    PubMed

    Liu, Xuan; Li, Shayu; Feng, Jiao; Li, Yi; Yang, Guoqiang

    2014-03-14

    A novel triarylboron compound, MPB, exhibiting reversible thermochromic dual-fluorescence in solid-state polymers and in liquid solvents was designed and synthesized. The fluorescent solid-state polymer with MPB can serve as a highly sensitive self-reference temperature indicator with a concentration independent feature. PMID:24481478

  15. Status of solid polymer fuel cell system development

    NASA Astrophysics Data System (ADS)

    Shoesmith, J. P.; Collins, R. D.; Oakley, M. J.; Stevenson, D. K.

    1994-04-01

    Solid polymer fuel cell (SPFC) systems are expected to see service in a wide variety of applications, including road vehicles, trains, ships, undersea power, and small scale stationary power generation. Each application brings unique requirements in terms of fuel, power, efficiency, volume and weight and, consequently, SPFC systems are expected to take a variety of forms. This paper reviews the development issues which must be resolved before SPFC systems can enter commercial service. It includes the results of system studies completed by Rolls-Royce and Associates during the last two years. Development priorities are highlighted, particularly for the stack and fuel processing system. Results of the testing of a novel compact fuel processing system are presented.

  16. [Rapid fabrication of molecularly imprinted polymer fibers for solid phase microextraction of bisphenol A].

    PubMed

    Hu, Mei; Zhang, Yijun; Yang, Jinghua; Zhou, Xiaomao; Wei, Zhuqing; Ding, Xiaoqing; Zhang, Yuping

    2015-02-01

    The rapid preparation of molecularly imprinted polymer (MIP) fibers was reported using bisphenol A (BPA) as the template molecular, acetonitrile (ACN) as the porogenic solvent, α-methacrylic acid (MAA) as the functional monomer, ethylene dimethacrylate (EDMA) as the crosslinker, and azodiisobutyronitrile (AIBN) as the thermal initiator. It was carried out within a capillary of 530 µm inner diameter (I. D.) by microwave irradiation in 7 min. The resulted BPA-MIP fibers were pushed out from the capillary, eluted in a vial and inserted in the capillary again followed by the application of the solid phase microextraction (SPME) procedure. The extraction performance was investigated in detail by varying the molar ratios between the template and the monomer (BPA/MAA), the concentration of NaCl, the extraction and desorption time, the pH value and the desorption solvents. The selectivity of the prepared MIP and non-molecularly imprinted polymer (NIP) fibers was comparatively evaluated by selecting two structurally-related compounds, phenol (P) and 4-phenylphenol (PP), and non-analogue dicyandiamide (DCD). The established method was successfully applied for the pretreatment and determination of BPA from beverage samples coupled to high performance liquid chromatography (HPLC). Under the optimal conditions, the linear range of BPA was 10-400 µg/L; the detection limit (LOD) was 0.45 µg/L and the recoveries spiked in the mineral water were 88.4%-102. 8%. The results demonstrated that the developed method can determine BPA in real samples with some advantages of simple pretreatment, rapid analysis, low limit of detection and low consumption of materials. PMID:25989683

  17. Simulation of interfacial fracture in highly crosslinked adhesives

    SciTech Connect

    STEVENS,MARK J.

    2000-05-22

    The fracture of highly-crosslinked networks is investigated by molecular dynamics simulations. The network is modeled as a bead-spring polymer network between two solid surfaces. The network is dynamically formed by crosslinking an equilibrated liquid mixture. Tensile pull fracture is simulated as a function of the number of interracial bonds. The sequence of molecular structural deformations that lead to failure are determined, and the connectivity is found to strongly control the stress-strain response and failure modes. The failure strain is related to the minimal paths in the network that connect the two solid surfaces. The failure stress is a fraction of the ideal stress required to fracture all the interracial bonds, and is linearly proportional to the number of interracial bonds. By allowing only a single bond between a crosslinker and the surface, interracial failure always occurs. Allowing up to half of the crosslinker's bonds to occur with the surface, cohesive failure can occur.

  18. Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

    DOE PAGESBeta

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; Ren, Fei; Keum, Jong Kahk; Ahn, Suk-Kyun; Li, Dawen; Chen, Jihua

    2015-08-06

    Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

  19. Investigation of Polymer-Surfactant and Polymer-Drug-Surfactant Miscibility for Solid Dispersion.

    PubMed

    Gumaste, Suhas G; Gupta, Simerdeep Singh; Serajuddin, Abu T M

    2016-09-01

    In a solid dispersion (SD), the drug is generally dispersed either molecularly or in the amorphous state in polymeric carriers, and the addition of a surfactant is often important to ensure drug release from such a system. The objective of this investigation was to screen systematically polymer-surfactant and polymer-drug-surfactant miscibility by using the film casting method. Miscibility of the crystalline solid surfactant, poloxamer 188, with two commonly used amorphous polymeric carriers, Soluplus® and HPMCAS, was first studied. Then, polymer-drug-surfactant miscibility was determined using itraconazole as the model drug, and ternary phase diagrams were constructed. The casted films were examined by DSC, PXRD and polarized light microscopy for any crystallization or phase separation of surfactant, drug or both in freshly prepared films and after exposure to 40°C/75% RH for 7, 14, and 30 days. The miscibility of poloxamer 188 with Soluplus® was <10% w/w, while its miscibility with HPMCAS was at least 30% w/w. Although itraconazole by itself was miscible with Soluplus® up to 40% w/w, the presence of poloxamer drastically reduced its miscibility to <10%. In contrast, poloxamer 188 had minimal impact on HPMCAS-itraconazole miscibility. For example, the phase diagram showed amorphous miscibility of HPMCAS, itraconazole, and poloxamer 188 at 54, 23, and 23% w/w, respectively, even after exposure to 40°C/75% RH for 1 month. Thus, a relatively simple and practical method of screening miscibility of different components and ultimately physical stability of SD is provided. The results also identify the HPMCAS-poloxamer 188 mixture as an optimal surface-active carrier system for SD. PMID:27301752

  20. A semi-empirical model to simplify the synthesis of homogeneous and transparent cross-linked polymers and their application in the preparation of optical sensing films.

    PubMed

    Medina-Castillo, Antonio L; Fernandez-Sanchez, Jorge F; Segura-Carretero, Antonio; Fernandez-Gutierrez, Alberto

    2009-10-15

    We propose a simple, semi-empirical model based on Hansen's solubility parameters for simplifying the synthesis and the optimization of homogeneous and transparent cross-linked polymers in order to obtain optical sensing films. More than 740 experiments were undertaken to demonstrate the reliability of the model and several applications are proposed. We have demonstrated that our model can help in the synthesis and optimization (percentage of cross-linker, changes in hydrophilicity, selection of porogens, quantity of template etc.) of homogeneous and transparent MIPs and NIPs (molecularly imprinted polymers) with VOCs; after the synthesis of 440 polymers in the homogeneity zone only 4.32% of them (19 samples out of 440) were heterogeneous. We suggest a role for its use in the development of novel polymeric resins for detecting volatile organic compounds in water by measuring intrinsic fluorescence, in simplifying the synthesis of imprinted polymers and in decreasing the number of experiments required to optimize optical sensing membranes. In addition, it might also be used for synthesizing and optimizing MIPs with a non-volatile template. PMID:19717295

  1. Construction of Covalent Organic Nanotubes by Light-Induced Cross-Linking of Diacetylene-Based Helical Polymers.

    PubMed

    Maeda, Kaho; Hong, Liu; Nishihara, Taishi; Nakanishi, Yusuke; Miyauchi, Yuhei; Kitaura, Ryo; Ousaka, Naoki; Yashima, Eiji; Ito, Hideto; Itami, Kenichiro

    2016-08-31

    Organic nanotubes (ONTs) are tubular nanostructures composed of small molecules or macromolecules that have found various applications including ion sensor/channels, gas absorption, and photovoltaics. While most ONTs are constructed by self-assembly processes based on weak noncovalent interactions, this unique property gives rise to the inherent instability of their tubular structures. Herein, we report a simple "helix-to-tube" strategy to construct robust, covalent ONTs from easily accessible poly(m-phenylene diethynylene)s (poly-PDEs) possessing chiral amide side chains that can adopt a helical conformation through hydrogen-bonding interactions. The helically folded poly-PDEs subsequently undergo light-induced cross-linking at longitudinally aligned 1,3-butadiyne moieties across the whole helix to form covalent tubes (ONTs) both in solution and solid phases. The structures of poly-PDEs and covalent ONTs were characterized by spectroscopic analyses, diffraction analysis, and microscopic analyses. We envisage that this simple yet powerful "helix-to-tube" strategy will generate a range of ONT-based materials by introducing functional moieties into a monomer. PMID:27486790

  2. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    PubMed

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now. PMID:23472763

  3. Preparation and application of sulfaguanidine-imprinted polymer on solid-phase extraction of pharmaceuticals from water.

    PubMed

    Mutavdžić Pavlović, Dragana; Nikšić, Korana; Livazović, Sara; Brnardić, Ivan; Anžlovar, Alojz

    2015-01-01

    The molecularly imprinted polymers (MIPs) with sulfaguanidine as a template, methacrylic acid, 4-vinylpyridine, and 2-hydroxyethyl methacrylate as functional monomers, ethylene glycol dimethacrylate as a cross-linker and 2,2'-azobis-isobutyronitrile as an initiator have been prepared through the cross-link reaction of polymerization. Solid-phase extraction (SPE) procedure for the extraction of sulfaguanidine from water samples using the prepared MIPs and non-imprinted (NIPs) was evaluated. The best MIP in combination with commercial sorbents was applied for simultaneous extraction of eight pharmaceuticals. New SPE cartridges were prepared by combination of optimal produced MIP and Oasis HLB in 6 mL of polypropilene SPE reservoir. The developed method which includes new SPE cartridge (MIPMAA-Oasis HLB, 400mg/6 mL) and thin-layer chromatography was validated. The method provides a linear response over the concentration range of 0.5-150 μg/L, depending on the pharmaceutical with the correlation coefficients>0.9843 in all cases except for norfloxacin (0.9770) and penicillin G procaine (0.9801). Also, the method has revealed low limits of detection (0.25-20 μg/L), good precision (intra and inter-day), a relative standard deviation below 15% and recoveries above 95% for all eight pharmaceuticals. The developed method by using newly prepared SPE cartridge has been successfully applied to the analysis of production wastewater samples from pharmaceutical industry. PMID:25281079

  4. Anhydrous state proton and lithium ion conducting solid polymer electrolytes based on sulfonated bisphenol-A-poly(arylene ethers)

    NASA Astrophysics Data System (ADS)

    Guha Thakurta, Soma

    Sulfonated polymer based solid polymer electrolytes (SPEs) have received considerable interest in recent years because of their wide variety of applications particularly in fuel cells, batteries, supercapacitors, and electrochromic devices. The present research was focused on three interrelated subtopics. First, two different bisphenol-A-poly(arylene ethers), polyetherimide (PEI) and polysulfone (PSU) were sulfonated by a post sulfonation method to various degrees of sulfonation, and their thermal and mechanical properties were examined. The effects of poly(arylene ether) chemical structure, reaction time, concentration, and types of sulfonating agents on sulfonation reaction were investigated. It was found that deactivation of bisphenol A unit caused by the electron withdrawing imide, retarded the sulfonation of PEI compared to PSU. Sulfonation conducted with a high concentration of sulfonating agent and/or prolonged reaction time exhibited evidence of degradation at the isopropylidene unit. The degradation occurred through the same mechanistic pathway with the two different sulfonating agents, chlorosulfonic acid (CSA) and trimethylsilyl chlorosulfonate (TMSCS). The degradation was faster with CSA than its silyl ester, TMSCS, and was evident even at low acid concentration. Second, novel anhydrous proton conducting solid polymer electrolytes (SPEs) were prepared by the incorporation of 1H-1,2,4-triazole (Taz) as a proton solvent in sulfonated polyetherimide (SPEI) matrix. The size, shape, and state of dispersion (crystal morphology) of triazole crystals in SPEI were examined as a function of degree of sulfonation and triazole concentration. Increasing sulfonic acid content caused reduction of triazole crystallite size, hence the depression of melting temperature and their uniform distribution throughout the sulfonated polymer matrix. The increased rate of structure diffusion within the smaller size crystals due to the improved molecular mobility contributed

  5. Thermally crosslinked polymeric compositions and methods of making the same

    DOEpatents

    Koros, William John; Kratochvil, Adam Michal

    2014-03-04

    The various embodiments of the present disclosure relate generally to thermally crosslinked polymeric compositions and methods of making thermally crosslinked polymeric compositions. An embodiment of the present invention comprises a composition comprising: a first polymer comprising a first repeat unit, the first repeat unit comprising a carboxyl group, wherein the first polymer crosslinks to a second polymer formed from a second repeat unit, and wherein the first polymer crosslinks to the second polymer without formation of an ester group.

  6. Improvement of surface lubricity of polymers and metals by a glow-discharge plasma cross-linking process.

    PubMed

    Chen, Meng; Hsieh, Ting-Ting; Osaki, Shigemasa; Zamora, Paul O; Tsang, Ray

    2009-01-01

    A plasma cross-linking process was employed to improve the surface lubricity of different types of biomaterials, including stainless steel (SS), nitinol, polyethylene and nylon. To investigate the influence of monomers containing double bonds on top-layer cross-linking of poly(ethylene oxide) compound (PEOC), five different monomers, N-trimethylsilyl-allylamine (TMSAA), ethylene, propylene, allyl alcohol and ethane, were used in the study to produce a cross-linked coating layer on sample surfaces. Before the plasma cross-linking, samples underwent plasma treatment followed by wet chemical coating. The plasma treatment consists of plasma etching in NH(3)/O(2), Tetramethylcyclo-tetrasiloxane (TMCTS) coating and TMSAA grafting. The wet coating process includes dip-coating in a solution of poly(oxyethylene)-compound bis(1-hydroxy-benzotriazolyl carbonate) (HPEOC), then dip-coating in a solution of PEOC. By application of plasma processing, HPEOC and PEOC wet coating to sample surfaces, the lubricity was increased by 83% compared to clean samples. The plasmas of TMSAA, ethylene, propylene and allyl alcohol, all containing a C=C double bond, produced a cross-linking layer on the PEOC surface. Consequently the surface lubricity was improved by 20% to 37% in comparison to no cross-linking. The favorable condition for plasma cross-linking was found to be high power and long time. Ethane plasma also reduced the pulling force although it has no double bond in the molecular structure, which indicated a thin plasma coating from saturated hydrocarbons deposited on HPEOC or PEOC surfaces could also cause cross-linking and improve lubricity. It was found that the TMSAA cross-linking also worked on HPEOC and HEPOC/PEOC, even though the prior plasma coating process was skipped. PMID:19228451

  7. Long-lasting solid-polymer electrolytic hygrometer

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.

    1978-01-01

    Device consists of hollow tube node of oxidation-resistant sulfonated fluorocarbon polymer. Tube absorbs moisture from air passing across inner and outer surfaces, causing change in polymer conductance. Change is related to change in water content in gas sample.

  8. Effect of polyacrylonitrile on triethylene glycol diacetate-2-propenoic acid butyl ester gel polymer electrolytes with interpenetrating crosslinked network for flexible lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Qiujun; Song, Wei-Li; Fan, Li-Zhen; Shi, Qiao

    2015-11-01

    A new flexible gel polymer electrolytes (GPE) with interpenetrating cross-linked network is fabricated by blending long-chain polyacrylonitrile (PAN) polymer matrix and short-chain triethylene glycol diacetate-2-propenoic acid butyl ester (TEGDA-BA) framework, with the purpose of enhancing the mechanical stability of the GPE frameworks via synergistic effects of the linear polymers and crosslinked monomers. The as fabricated frameworks enable the liquid electrolytes to be firmly entrapped in the polymeric matrices, which significantly improves the mechanical bendability and interface stability of the resultant GPE. The GPE with 5 wt% PAN exhibits high ionic conductivity up to 5.9 × 10-3 S cm-1 at 25 °C with a stable electrochemical window observed (>5.0 V vs. Li/Li+). The Li|GPE|LiFePO4 half cells demonstrate remarkably stable capacity retention and rate ability during cycling tests. As expected, the LiFePO4|GPE|Li4Ti5O12 full cells also exhibit discharge capacity of 125.2 mAh g-1 coupled with high columbic efficiency greater than 98% after 100 cycles. The excellent mechanical flexibility and charge/discharge performance suggest that the GPE holds great application potential in flexible LIBs.

  9. Automated solid-phase radiofluorination using polymer-supported phosphazenes.

    PubMed

    Mathiessen, Bente; Zhuravlev, Fedor

    2013-01-01

    The polymer supported phosphazene bases PS-P₂(tBu) and the novel PS-P₂(PEG) allowed for efficient extraction of [¹⁸F]F⁻ from proton irradiated [¹⁸O]H₂O and subsequent radiofluorination of a broad range of substrates directly on the resin. The highest radiochemical yields were obtained with aliphatic sulfonates (69%) and bromides (42%); the total radiosynthesis time was 35-45 min. The multivariate analysis showed that the radiochemical yields and purities were controlled by the resin load, reaction temperature, and column packing effects. The resins could be reused several times with the same or different substrates. The fully automated on-column radiofluorination methodology was applied to the radiosynthesis of the important PET radiotracers [¹⁸F]FLT and [¹⁸F]FDG. The latter was produced with 40% yield on a 120 GBq scale and passed GMP-regulated quality control required for commercial production of [1¹⁸F]FDG. The combination of compact form factor, simplicity of [¹⁸F]F⁻ recovery and processing, and column reusability can make solid phase radiofluorination an attractive radiochemistry platform for the emerging dose-on-demand instruments for bedside production of PET radiotracers. PMID:23999726

  10. Compact hydrogen production systems for solid polymer fuel cells

    NASA Astrophysics Data System (ADS)

    Ledjeff-Hey, K.; Formanski, V.; Kalk, Th.; Roes, J.

    Generally there are several ways to produce hydrogen gas from carbonaceous fuels like natural gas, oil or alcohols. Most of these processes are designed for large-scale industrial production and are not suitable for a compact hydrogen production system (CHYPS) in the power range of 1 kW. In order to supply solid polymer fuel cells (SPFC) with hydrogen, a compact fuel processor is required for mobile applications. The produced hydrogen-rich gas has to have a low level of harmful impurities; in particular the carbon monoxide content has to be lower than 20 ppmv. Integrating the reaction step, the gas purification and the heat supply leads to small-scale hydrogen production systems. The steam reforming of methanol is feasible at copper catalysts in a low temperature range of 200-350°C. The combination of a small-scale methanol reformer and a metal membrane as purification step forms a compact system producing high-purity hydrogen. The generation of a SPFC hydrogen fuel gas can also be performed by thermal or catalytic cracking of liquid hydrocarbons such as propane. At a temperature of 900°C the decomposition of propane into carbon and hydrogen takes place. A fuel processor based on this simple concept produces a gas stream with a hydrogen content of more than 90 vol.% and without CO and CO2.

  11. Microencapsulation of liquid and solid substances by reactive polymers.

    PubMed

    Shevchuk, O; Serdiuk, V; Bukartyk, N; Moncibovich, R; Tokarev, V

    2014-01-01

    This study is devoted to the development of techniques for the formation of polymeric microcapsules (MC) with either liquid or solid core and with the polymer shell containing diverse functional groups on the basis of new reactive functional copolymers (FC). Two approaches to the formation of MC containing FC shell that included the stages of "oil-in-water" or "water-in-oil" dispersion preparation followed by slow extraction of solvents from dispersed phase by dispersive media were examined. FC with the same structure was successfully applied for both "oil-in-water" and "water-in-oil" systems. Spherical MC with the liquid hydrocarbon core demonstrated essential increase in their volume after heating at the temperature exceeding a boiling point of hydrocarbon encapsulated. Presence of reactive groups in the MC shell opens up new opportunity for further tuning the MC properties via their interaction with proper compounds, particularly via graft-polymerisation of diverse vinyl monomers initiated from the MC surface. PMID:24697175

  12. Molecularly imprinted polymer on a SiO2 -coated graphene oxide surface for the fast and selective dispersive solid-phase extraction of Carbamazepine from biological samples.

    PubMed

    Khalilian, Faezeh; Ahmadian, Setareh

    2016-04-01

    A surface carbamazepine-imprinted polymer was grafted and synthesized on the SiO2 /graphene oxide surface. Firstly SiO2 was coated on synthesized graphene oxide sheet using the sol-gel technique. Prior to polymerization, the vinyl group was incorporated on to the surface of SiO2 /graphene oxide to direct selective polymerization on the surface. Methacrylic acid, ethylene glycol dimethacrylate and ethanol were used as monomer, cross-linker and porogen, respectively. Nonimprinted polymer was also prepared for comparison. The properties of the molecularly imprinted polymer were characterized using field-emission scanning electron microscopy and Fourier-transform infrared spectroscopy. The surface molecularly imprinted polymer was utilized as an adsorbent of dispersive solid-phase extraction for separation and preconcentration of carbamazepine. The effects of the different parameters influencing the extraction efficiency, such as sample pH were investigated and optimized. The specificity of the molecular imprinted polymer over the nonimprinted polymer was examined in absence and presence of competitive drugs. The carbamazepine calibration curve showed linearity in the ranges 0.5-500 μg/L. The limits of detection and quantification under the optimized conditions were 0.1 and 0.3 μg/L, respectively. The within-day and between-day relative standard deviations (n = 3) were 3.6 and 4.3%, respectively. Furthermore, the relative recoveries for spiked biological samples were above 85%. PMID:26899307

  13. Characterization of Solid Polymers, Ceramic Gap Filler, and Closed-Cell Polymer Foam Using Low-Load Test Methods

    NASA Technical Reports Server (NTRS)

    Herring, Helen M.

    2008-01-01

    Various solid polymers, polymer-based composites, and closed-cell polymer foam are being characterized to determine their mechanical properties, using low-load test methods. The residual mechanical properties of these materials after environmental exposure or extreme usage conditions determines their value in aerospace structural applications. In this experimental study, four separate polymers were evaluated to measure their individual mechanical responses after thermal aging and moisture exposure by dynamic mechanical analysis. A ceramic gap filler, used in the gaps between the tiles on the Space Shuttle, was also tested, using dynamic mechanical analysis to determine material property limits during flight. Closed-cell polymer foam, used for the Space Shuttle External Tank insulation, was tested under low load levels to evaluate how the foam's mechanical properties are affected by various loading and unloading scenarios.

  14. Development of two-stage solidification technology for implementing micro structures with liquid magnetic polymer and solid magnetic anisotropic polymer

    NASA Astrophysics Data System (ADS)

    Hsu, Fu-Ming; Fang, Weileun

    2014-09-01

    This study presents two-stage solidification technology for fabricating micromagnetic polymer composite (MPC, polymer with magnetic particles) structures. In this process, ultra-violet (UV)-light polymer curing is used for the first stage of MPC solidification. The surface of the MPC structure is solidified in this step. Moreover, thermal polymer curing is employed for the second stage of MPC solidification. The second stage of curing was mainly for the body solidification of the MPC. The distribution of magnetic particles in MPC can be specified by applying a magnetic field during the second solidification process. Based on the presented process technologies, microstructures with liquid MPC (NdFeB particles of different wt% in liquid polymer), isotropic solid MPC and anisotropic solid MPC have been demonstrated. Microdevices with liquid MPC embedded in solid micro balls and thin layers are also demonstrated. Various tests are performed to characterize the magnetic properties of the fabricated micro MPC structures. Measurements show that the fabricated solid MPC has reasonable coercivity, as compared with bulk materials. However, the remanence and the saturation magnetization still need to be improved.

  15. Cross-linking characterization of polymers based on their optical dispersion utilizing a white-light interferometer

    NASA Astrophysics Data System (ADS)

    Taudt, Ch.; Baselt, T.; Oreski, G.; Hirschl, Ch.; Koch, E.; Hartmann, P.

    2015-05-01

    This work analyses samples of the widely used encapsulant of photovoltaics modules, ethylene vinyl acetate (EVA). The samples were cross-linked using a lamination technique for different curing times (0 - 20 minutes). The cross-linking characterization is done by determinating the material dispersion with the aid of a combined temporal- and spectral domain white-light interferometer. With the proposed technique it was possible to discriminate the differences in crosslinking for the given curing times. One important feature of this approach is the possibility to perform space resolved measurements of the crosslinking state with μm-resolution. Furthermore the paper discusses the mathematical analysis and processing of measurement data and shows a prototype solution for the fast and automated data acquisition for industrial application.

  16. Dye-sensitized solar cell comprising polyethyl methacrylate doped with ammonium iodide solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Vivek Kr.; Bhattacharya, B.; Shukla, S.; Singh, Pramod K.

    2014-09-01

    The aim of the present work was to develop a new solid electrolyte polyethyl methacrylate doped with ammonium iodide polymer electrolyte and its application in dye-sensitized solar cell (DSSC). The electrical, structural and photoelectrochemical properties of polymer electrolytes are presented in detail. DSSCs have been fabricated and characterized. The polymer electrolyte film with maximum ionic conductivity shows maximum efficient DSSC of efficiency 0.43 % at 1 sun condition.

  17. Dye-sensitized solar cell comprising polyethyl methacrylate doped with ammonium iodide solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Vivek Kr.; Bhattacharya, B.; Shukla, S.; Singh, Pramod K.

    2015-03-01

    The aim of the present work was to develop a new solid electrolyte polyethyl methacrylate doped with ammonium iodide polymer electrolyte and its application in dye-sensitized solar cell (DSSC). The electrical, structural and photoelectrochemical properties of polymer electrolytes are presented in detail. DSSCs have been fabricated and characterized. The polymer electrolyte film with maximum ionic conductivity shows maximum efficient DSSC of efficiency 0.43 % at 1 sun condition.

  18. Solid-liquid separation of dairy manure with PAM and chitosan polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Organic polymers are useful to increase separation of suspended solids and carbon compounds from liquid swine manure, but experiences with dairy manure are limited. In this experiment, two polymers, a synthetic polyacrylamide (PAM) and a natural chitosan were used to increase separation of suspended...

  19. Peripherally cross-linking the shell of core-shell polymer micelles decreases premature release of physically loaded combretastatin A4 in whole blood and increases its mean residence time and subsequent potency against primary murine breast tumors after IV administration

    PubMed Central

    Wakaskar, Rajesh R.; Bathena, Sai Praneeth R.; Tallapaka, Shailendra; Ambardekar, Vishakha V.; Gautum, Nagsen; Thakare, Rhishikesh N.; Simet, Samantha M.; Curran, Stephen M.; Singh, Rakesh K.; Dong, Yuxiang

    2014-01-01

    Purpose Determine the feasibility and potential benefit of peripherally cross-linking the shell of core-shell polymer micelles on the premature release of physically loaded hydrophobic drug in whole blood and subsequent potency against solid tumors. Methods Individual Pluronic F127 polymer micelles (F127 PM) peripherally cross-linked with ethylenediamine at 76% of total PEO blocks (X-F127 PM) were physically loaded with combretastatin A4 (CA4) by the solid dispersion method and compared to CA4 physically loaded in uncross-linked F127 PM, CA4 in DMSO in vitro, or water-soluble CA4 phosphate (CA4P) in vivo. Results X-F127 PM had similar CA4 loading and aqueous solubility as F127 PM up to 10 mg CA4 / mL at 22.9 wt% and did not aggregate in PBS or 90% (v/v) human serum at 37°C for at least 24 h. In contrast, X-F127 PM decreased the unbound fraction of CA4 in whole blood (fu) and increased the mean plasma residence time and subsequent potency of CA4 against the vascular function and growth of primary murine 4T1 breast tumors over CA4 in F127 PM and water-soluble CA4P after IV administration. Conclusions Given that decreasing the fu is an indication of decreased drug release, peripherally cross-linking the shell of core-shell polymer micelles may be a simple approach to decrease premature release of physically loaded hydrophobic drug in the blood and increase subsequent potency in solid tumors. PMID:25223962

  20. pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli.

    PubMed

    Holten-Andersen, Niels; Harrington, Matthew J; Birkedal, Henrik; Lee, Bruce P; Messersmith, Phillip B; Lee, Ka Yee C; Waite, J Herbert

    2011-02-15

    Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) Advances in Insect Physiology: Insect Integument and Color, eds Jérôme C, Stephen JS (Academic Press, London), pp 75-133]. Coordination between Fe and catechol ligands has recently been correlated to the hardness and high extensibility of the cuticle of mussel byssal threads and proposed to endow self-healing properties [Harrington MJ, Masic A, Holten-Andersen N, Waite JH, Fratzl P (2010) Science 328:216-220]. Inspired by the pH jump experienced by proteins during maturation of a mussel byssus secretion, we have developed a simple method to control catechol-Fe(3+) interpolymer cross-linking via pH. The resonance Raman signature of catechol-Fe(3+) cross-linked polymer gels at high pH was similar to that from native mussel thread cuticle and the gels displayed elastic moduli (G') that approach covalently cross-linked gels as well as self-healing properties. PMID:21278337

  1. Coarse-Grained Molecular Dynamics Study of the Curing and Properties of Highly Cross-Linked Epoxy Polymers.

    PubMed

    Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

    2016-09-01

    In this work, a coarse-grained model is developed for highly cross-linked bisphenol A diglycidyl ether epoxy resin with diaminobutane hardener. In this model, all conformationally relevant coarse-grained degrees of freedom are accounted for by sampling over the free-energy surfaces of the atomic structures using quantum mechanical simulations. The interaction potentials between nonbonded coarse-grained particles are optimized to accurately predict the experimentally measured density and glass-transition temperature of the system. In addition, a new curing algorithm is also developed to model the creation of highly cross-linked epoxy networks. In this algorithm, to create a highly cross-linked network, the reactants are redistributed from regions with an excessive number of reactive molecules to regions with a lower number of reactants to increase the chances of cross-linking. This new algorithm also dynamically controls the rate of cross-linking at each local region to ensure uniformity of the resulting network. The curing simulation conducted using this algorithm is able to develop polymeric networks having a higher average degree of cross-linking, which is more uniform throughout the simulation cell as compared to that in the networks cured using other curing algorithms. The predicted gel point from the current curing algorithm is in the acceptable theoretical and experimental range of measured values. Also, the resulting cross-linked microstructure shows a volume shrinkage of 5%, which is close to the experimentally measured volume shrinkage of the cured epoxy. Finally, the thermal expansion coefficients of materials in the glassy and rubbery states show good agreement with the experimental values. PMID:27504803

  2. Selective solid-phase extraction using molecularly imprinted polymer as a sorbent for the analysis of fenarimol in food samples.

    PubMed

    Khan, Shagufta; Bhatia, Tejasvi; Trivedi, Purushottam; Satyanarayana, G N V; Mandrah, Kapil; Saxena, Prem Narayan; Mudiam, Mohana Krishna Reddy; Roy, Somendu Kumar

    2016-05-15

    In the present communication, a non-covalent fenarimol-imprinted polymer was synthesized by precipitation polymerization technique using methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, and azobisisobutyronitrile (AIBN) as an initiator in different porogenic solvent. Binding study of molecularly imprinted and non-imprinted polymer (MIP and NIP) showed that MIP possesses a higher affinity towards this analyte compared to NIP. The binding affinity of MIP was calculated by static and kinetic adsorption study. Further, a MIP based cartridge was designed to use in extraction process, necessary for specific determination and quantification of the fungicide in food matrices. Under the optimum conditions, developed method was found to be linear (R(2)=0.9999-0.9994). Limit of detection (LOD) and limit of quantitation (LOQ) in samples were 0.03-0.06 and 0.12-0.21 μg mL(-1), respectively. The rate of recovery of fenarimol was 91.16-99.52% on MIPs. The validated method of molecularly imprinted solid-phase extraction (MISPE) cartridge was successfully applied to the food matrices and compared with commercial sorbent (RP18 and Oasis HLB). However we feel, this method has promising applications in the routine analysis of food samples in industry. PMID:26776046

  3. Solid-like rheological response of non-entangled polymers in the molten state.

    PubMed

    Mendil, H; Baroni, P; Noirez, L

    2006-01-01

    We show that non-entangled polymers display an elastic-like behaviour at a macroscopic scale (probed at some 0.100 mm thickness) up to at least hundred degrees above the glass transition temperature. This observation, found under non-slippage conditions, both for side-chain liquid crystalline polymers and ordinary polymers, is in contradiction with the typically found flow behaviour of polymer melt. Our measurements were carried out with a conventional rheometer at thicknesses of several tenths millimetres. Thus, we were probing bulk properties. The observed elasticity supposedly implies that even in the melt the chains experience a cohesive effect of macroscopic distances, involving collective motions over time scales longer than the individual relaxation time of an individual polymer chain. The detection of such a solid-like property of molten non-entangled polymers is of considerable importance for a better understanding of the polymer dynamics. PMID:16432635

  4. Solid-like rheological response of non-entangled polymers in the molten state

    NASA Astrophysics Data System (ADS)

    Mendil, H.; Baroni, P.; Noirez, L.

    2006-01-01

    We show that non-entangled polymers display an elastic-like behaviour at a macroscopic scale (probed at some 0.100;mm thickness) up to at least hundred degrees above the glass transition temperature. This observation, found under non-slippage conditions, both for side-chain liquid crystalline polymers and ordinary polymers, is in contradiction with the typically found flow behaviour of polymer melt. Our measurements were carried out with a conventional rheometer at thicknesses of several tenths millimetres. Thus, we were probing bulk properties. The observed elasticity supposedly implies that even in the melt the chains experience a cohesive effect of macroscopic distances, involving collective motions over time scales longer than the individual relaxation time of an individual polymer chain. The detection of such a solid-like property of molten non-entangled polymers is of considerable importance for a better understanding of the polymer dynamics.

  5. A Cross-Linking Succinonitrile-Based Composite Polymer Electrolyte with Uniformly Dispersed Vinyl-Functionalized SiO2 Particles for Li-Ion Batteries.

    PubMed

    Liu, Kai; Ding, Fei; Liu, Jiaquan; Zhang, Qingqing; Liu, Xingjiang; Zhang, Jinli; Xu, Qiang

    2016-09-14

    A cross-linking succinonitrile (SN)-based composite polymer electrolyte (referred to as "CLPC-CPE"), in which vinyl-functionalized SiO2 particles connect with trimethylolpropane propoxylate triacrylate (TPPTA) monomers by covalent bonds, was prepared by an ultraviolet irradiation (UV-curing) process successfully. Vinyl-functionalized SiO2 particles may react with TPPTA monomers to form a cross-linking network within the SN-based composite polymer electrolyte under ultraviolet irradiation. Vinyl-functionalized SiO2 particles as the fillers of polymer electrolyte may improve both the thermal stability of CLPC-CPE and interfacial compatibility between CLPC-CPE and electrodes effectively. There is no weight loss for CLPC-CPE until above 230 °C. The ionic conductivity of CLPC-CPE may reach 7.02 × 10(-4) S cm(-1) at 25 °C. CLPC-CPE has no significant oxidation current until up to 4.6 V (vs Li/Li(+)). The cell of LiFePO4/CLPC-CPE/Li has presented superior cycle performance and rate capability. The cell of LiFePO4/CLPC-CPE/Li may deliver a high discharge capacity of 154.4 mAh g(-1) at a rate of 0.1 C after 100 charge-discharge cycles, which is similar than that of the control cell of LiFePO4/liquid electrolyte/Li. Furthermore, the cell of LiFePO4/CLPC-CPE/Li can display a high discharge capacity of 112.7 mAh g(-1) at a rate of 2 C, which is higher than that of the cells assembled with other plastic crystal polymer electrolyte reported before obviously. PMID:27561892

  6. Self-replenishing ability of cross-linked low surface energy polymer films investigated by a complementary experimental-simulation approach

    SciTech Connect

    Esteves, A. C. C. E-mail: g.dewith@tue.nl; Lyakhova, K.; Riel, J. M. van; With, G. de E-mail: g.dewith@tue.nl; Ven, L. G. J. van der; Benthem, R. A. T. M. van

    2014-03-28

    Nowadays, many self-healing strategies are available for recovering mechanical damage of bulk polymeric materials. The recovery of surface-dependent functionalities on polymer films is, however, equally important and has been less investigated. In this work we study the ability of low surface energy cross-linked poly(ester urethane) networks containing perfluorinated dangling chains to self-replenish their surface, after being submitted to repeated surface damage. For this purpose we used a combined experimental-simulation approach. Experimentally, the cross-linked films were intentionally damaged by cryo-microtoming to remove top layers and create new surfaces which were characterized by water Contact Angle measurements and X-Ray Photoelectron Spectroscopy. The same systems were simultaneously represented by a Dissipative Particles Dynamics simulation method, where the damage was modeled by removing the top film layers in the simulation box and replacing it by new “air” beads. The influence of different experimental parameters, such as the concentration of the low surface energy component and the molecular mobility span of the dangling chains, on the surface recovery is discussed. The combined approach reveals important details of the self-replenishing ability of damaged polymer films such as the occurrence of multiple-healing events, the self-replenishing efficiency, and the minimum “healing agent” concentration for a maximum recovery.

  7. Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

    PubMed

    Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

    2015-10-21

    We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli. PMID:26426303

  8. Self-replenishing ability of cross-linked low surface energy polymer films investigated by a complementary experimental-simulation approach.

    PubMed

    Esteves, A C C; Lyakhova, K; van Riel, J M; van der Ven, L G J; van Benthem, R A T M; de With, G

    2014-03-28

    Nowadays, many self-healing strategies are available for recovering mechanical damage of bulk polymeric materials. The recovery of surface-dependent functionalities on polymer films is, however, equally important and has been less investigated. In this work we study the ability of low surface energy cross-linked poly(ester urethane) networks containing perfluorinated dangling chains to self-replenish their surface, after being submitted to repeated surface damage. For this purpose we used a combined experimental-simulation approach. Experimentally, the cross-linked films were intentionally damaged by cryo-microtoming to remove top layers and create new surfaces which were characterized by water Contact Angle measurements and X-Ray Photoelectron Spectroscopy. The same systems were simultaneously represented by a Dissipative Particles Dynamics simulation method, where the damage was modeled by removing the top film layers in the simulation box and replacing it by new "air" beads. The influence of different experimental parameters, such as the concentration of the low surface energy component and the molecular mobility span of the dangling chains, on the surface recovery is discussed. The combined approach reveals important details of the self-replenishing ability of damaged polymer films such as the occurrence of multiple-healing events, the self-replenishing efficiency, and the minimum "healing agent" concentration for a maximum recovery. PMID:24697476

  9. Solid-state, rechargeable Li/LiFePO 4 polymer battery for electric vehicle application

    NASA Astrophysics Data System (ADS)

    Damen, L.; Hassoun, J.; Mastragostino, M.; Scrosati, B.

    A solid-state polymer lithium metal battery having a LiFePO 4/C composite cathode and a poly(ethylene oxide) PEO-based solid polymer electrolyte was assembled and characterized in terms of specific energy and power according to the protocol for electric vehicle (EV) application set by the USABC-DOE. The results of these tests show that this polymer battery surpasses the goals stated by USABC-DOE and, hence, may be suitable for application in the evolving EV market.

  10. Ionically conducting polymers: Principles and properties of solid electrolytes

    SciTech Connect

    Skotheim, T.; Okamoto, Y.

    1987-01-01

    The recent success in developing rechargeable lithium batteries incorporating polyether-based electrolytes has led to the anticipation of a wider use of polymer electrolytes in a host of different applications. The polymers with the best combinations of solvation power, conductivity and electrochemical stability are all based on either PEO or polymers incorporating a high density of EO units. PEO-based electrolytes still yield the highest conductivities at elevated temperatures (approx.100/sup 0/C) when it is completely amorphous. What has emerged during the last ten years of research on polymer electrolytes is the central importance of the amorphous state for high conductivity, where the ion mobility is governed by the mobility associated with a low glass transition temperature. The difference between polymer and liquid electrolytes is that in the former the solvating part does not migrate with the ions. There is, however, still some controversy concerning the nature of the ionic species, i.e. whether the salt is present in the form of associated ions. The intensive research of the last few years has led to a far better understanding of these polymer-ion complexes. Several different types of solvating polymers have been developed, in particular single ion conductors, which represent much of the future of ion conducting polymer research. 36 refs.

  11. Cross-linked branching nanohybrid polymer electrolyte with monodispersed TiO2 nanoparticles for high performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Ma, Cheng; Zhang, Jinfang; Xu, Mingquan; Xia, Qingbing; Liu, Jiatu; Zhao, Shuai; Chen, Libao; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

    2016-06-01

    Nanohybrid polymer electrolytes (NHPE) with ceramic particles have attracted significant attention owing to their improvement in electrochemical performance. However, particle aggregation and weak nanoparticle/polymer matrix interaction restrict their further application in lithium-ion batteries (LIBs). We demonstrate a facile in-situ polymerization/crystallization method to synthesize a homogeneous TiO2-grafted NHPE with a cross-linked branching structure, comprised of ion-conducting poly(ethylene glycol) methyl ether methacrylate (PEGMEM) and non-polar stearyl methacrylate (SMA). This technique is different from existing methods of blending functionalized ceramic particles into the polymer matrix. Highly monodispersed TiO2 nanocrystals enhance the effective interfacial interactions between particles and polymer matrix, which suppress the crystallization of ethylene oxide (EO) groups and facilitate forming continuously interconnected ion-conducting channels. Moreover, an increased dissociation degree of Li salt can also be achieved. The TiO2-grafted NHPE exhibits superior electrochemical properties with an ionic conductivity of 1.1 × 10-4 S cm-1 at 30 °C, a high lithium ion transference number and excellent interfacial compatibility with the lithium electrode. In particular, a lithium-ion battery based on TiO2-grafted NHPE demonstrates good C-rate performance, as well as excellent cycling stability with an initial discharge capacity of 153.5 mAh g-1 and a capacity retention of 96% after 300 cycles at 1 C (80 °C).

  12. Cross-linked supramolecular polymer gels constructed from discrete multi-pillar[5]arene metallacycles and their multiple stimuli-responsive behavior.

    PubMed

    Li, Zhong-Yu; Zhang, Yanyan; Zhang, Chang-Wei; Chen, Li-Jun; Wang, Chao; Tan, Hongwei; Yu, Yihua; Li, Xiaopeng; Yang, Hai-Bo

    2014-06-18

    A new family of discrete hexakis-pillar[5]arene metallacycles with different sizes have been successfully prepared via coordination-driven self-assembly, which presented very few successful examples of preparation of discrete multiple pillar[n]arene derivatives. These newly designed hexakis-pillar[5]arene metallacycles were well characterized with one-dimensional (1-D) multinuclear NMR ((1)H and (31) P NMR), two-dimensional (2-D) (1)H-(1)H COSY and NOESY, ESI-TOF-MS, elemental analysis, and PM6 semiempirical molecular orbital methods. Furthermore, the host-guest complexation of such hexakis-pillar[5]arene hosts with a series of different neutral ditopic guests G1-6 were well investigated. Through host-guest interactions of hexakis-pillar[5]arene metallacycles H2 or H3 with the neutral dinitrile guest G5, the cross-linked supramolecular polymers H2⊃(G5)3 or H3⊃(G5)3 were successfully constructed at the high-concentration region, respectively. Interestingly, these cross-linked supramolecular polymers transformed into the stable supramolecular gels upon increasing the concentrations to a relatively high level. More importantly, by taking advantage of the dynamic nature of metal-ligand bonds and host-guest interactions, the reversible multiple stimuli-responsive gel-sol phase transitions of such polymer gels were successfully realized under different stimuli, such as temperature, halide, and competitive guest, etc. The mechanism of such multiple stimuli-responsive processes was well illustrated by in situ multinuclear NMR investigation. This research not only provides a highly efficient approach to the preparation of discrete multiple pillar[n]arene derivatives but also presents a new family of multiple stimuli-responsive "smart" soft matters. PMID:24571308

  13. Solid Tumor-Targeting Theranostic Polymer Nanoparticle in Nuclear Medicinal Fields

    PubMed Central

    Makino, Akira; Kimura, Shunsaku

    2014-01-01

    Polymer nanoparticles can be prepared by self-assembling of amphiphilic polymers, and various types of molecular assemblies have been reported. In particular, in medicinal fields, utilization of these polymer nanoparticles as carriers for drug delivery system (DDS) has been actively tried, and some nanoparticulate drugs are currently under preclinical evaluations. A radionuclide is an unstable nucleus and decays with emission of radioactive rays, which can be utilized as a tracer in the diagnostic imaging systems of PET and SPECT and also in therapeutic purposes. Since polymer nanoparticles can encapsulate most of diagnostic and therapeutic agents with a proper design of amphiphilic polymers, they should be effective DDS carriers of radionuclides in the nuclear medicinal field. Indeed, nanoparticles have been recently attracting much attention as common platform carriers for diagnostic and therapeutic drugs and contribute to the development of nanotheranostics. In this paper, recent developments of solid tumor-targeting polymer nanoparticles in nuclear medicinal fields are reviewed. PMID:25379530

  14. Solid tumor-targeting theranostic polymer nanoparticle in nuclear medicinal fields.

    PubMed

    Makino, Akira; Kimura, Shunsaku

    2014-01-01

    Polymer nanoparticles can be prepared by self-assembling of amphiphilic polymers, and various types of molecular assemblies have been reported. In particular, in medicinal fields, utilization of these polymer nanoparticles as carriers for drug delivery system (DDS) has been actively tried, and some nanoparticulate drugs are currently under preclinical evaluations. A radionuclide is an unstable nucleus and decays with emission of radioactive rays, which can be utilized as a tracer in the diagnostic imaging systems of PET and SPECT and also in therapeutic purposes. Since polymer nanoparticles can encapsulate most of diagnostic and therapeutic agents with a proper design of amphiphilic polymers, they should be effective DDS carriers of radionuclides in the nuclear medicinal field. Indeed, nanoparticles have been recently attracting much attention as common platform carriers for diagnostic and therapeutic drugs and contribute to the development of nanotheranostics. In this paper, recent developments of solid tumor-targeting polymer nanoparticles in nuclear medicinal fields are reviewed. PMID:25379530

  15. All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes.

    PubMed

    Lago, Nerea; Garcia-Calvo, Oihane; Lopez del Amo, Juan Miguel; Rojo, Teofilo; Armand, Michel

    2015-09-21

    Lithium-based rechargeable batteries offer superior specific energy and power, and have enabled exponential growth in industries focused on small electronic devices. However, further increases in energy density, for example for electric transportation, face the challenge of harnessing the lithium metal as negative electrode instead of limited-capacity graphite and its heavy copper current collector. All-solid-state batteries utilize solid polymer electrolytes (SPEs) to overcome the safety issues of liquid electrolytes. We demonstrate an all-solid-state lithium-ion battery by using plasticized poly(ethylene oxide)-based SPEs comprising anions grafted or co-grafted onto ceramic nanoparticles. This new approach using grafted ceramic nanoparticles enables the development of a new generation of nanohybrid polymer electrolytes with high ionic conductivity as well as high electrochemical and mechanical stability, enabling Li-ion batteries with long cycle life. PMID:26373359

  16. Solid state drug-polymer miscibility studies using the model drug ABT-102.

    PubMed

    Jog, Rajan; Gokhale, Rajeev; Burgess, Diane J

    2016-07-25

    Amorphous solid dispersions typically suffer storage stability issues due to: their amorphous nature, high drug loading, uneven drug:stabilizer ratio and plasticization effects as a result of hygroscopic excipients. An extensive solid state miscibility study was conducted to aid in understanding the mechanisms involved in drug/stabilizer interactions. ABT-102 (model drug) and nine different polymers with different molecular weights and viscosities were selected to investigate drug/polymer miscibility. Three different polymer:drug ratios (1:3, 1:1 and 3:1, w/w) were analyzed using: DSC, FTIR and PXRD. Three different techniques were used to prepare the amorphous solid dispersions: serial dilution, solvent evaporation and spray drying. Spray drying was the best method to obtain amorphous solid dispersions. However, under certain conditions amorphous formulations could be obtained using solvent evaporation. Melting point depression was used to calculate interaction parameters and free energy of mixing for the various drug polymer mixtures. The spray dried solid dispersions yielded a negative free energy of mixing which indicated strong drug-polymer miscibility compared to the solvent evaporation and serial dilution method. Soluplus was the best stabilizer compared to PVP and HPMC, which is probably a consequence of strong hydrogen bonding between the two CO moieties of soluplus and the drug NH moieities. PMID:27265312

  17. Actively-targeted polyion complex micelles stabilized by cholesterol and disulfide cross-linking for systemic delivery of siRNA to solid tumors.

    PubMed

    Oe, Yusuke; Christie, R James; Naito, Mitsuru; Low, Stewart A; Fukushima, Shigeto; Toh, Kazuko; Miura, Yutaka; Matsumoto, Yu; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2014-09-01

    For small interfering RNA (siRNA)-based cancer therapies, we report an actively-targeted and stabilized polyion complex micelle designed to improve tumor accumulation and cancer cell uptake of siRNA following systemic administration. Improvement in micelle stability was achieved using two stabilization mechanisms; covalent disulfide cross-linking and non-covalent hydrophobic interactions. The polymer component was designed to provide disulfide cross-linking and cancer cell-targeting cyclic RGD peptide ligands, while cholesterol-modified siRNA (Chol-siRNA) provided additional hydrophobic stabilization to the micelle structure. Dynamic light scattering confirmed formation of nano-sized disulfide cross-linked micelles (<50 nm in diameter) with a narrow size distribution. Improved stability of Chol-siRNA-loaded micelles (Chol-siRNA micelles) was demonstrated by resistance to both the dilution in serum-containing medium and counter polyion exchange with dextran sulfate, compared to control micelles prepared with Chol-free siRNA (Chol-free micelles). Improved stability resulted in prolonged blood circulation time of Chol-siRNA micelles compared to Chol-free micelles. Furthermore, introduction of cRGD ligands onto Chol-siRNA micelles significantly facilitated accumulation of siRNA in a subcutaneous cervical cancer model following systemic administration. Ultimately, systemically administered cRGD/Chol-siRNA micelles exhibited significant gene silencing activity in the tumor, presumably due to their active targeting ability combined with the enhanced stability through both hydrophobic interactions of cholesterol and disulfide cross-linking. PMID:24930854

  18. 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.

  19. Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

    1989-01-01

    Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

  20. Synthesis and In Vivo Pharmacokinetic Evaluation of Degradable Shell Crosslinked Polymer Nanoparticles with Poly(carboxybetaine) vs. Poly(ethylene glycol) Surface-grafted Coatings

    PubMed Central

    Li, Ang; Luehmann, Hannah P.; Sun, Guorong; Samarajeewa, Sandani; Zou, Jiong; Zhang, Shiyi; Zhang, Fuwu; Welch, Michael J.; Liu, Yongjian; Wooley, Karen L.

    2012-01-01

    Nanoparticles with tunable pharmacokinetics are desirable for various biomedical applications. Poly(ethylene glycol) (PEG) is well known to create “stealth” effects to stabilize and extend the blood circulation of nanoparticles. In this work, poly(carboxybetaine) (PCB), a new non-fouling polymer material, was incorporated as surface-grafted coatings, conjugated onto degradable shell crosslinked knedel-like nanoparticles (dSCKs) composed of poly(acrylic acid)- based shells and poly(lactic acid) (PLA) cores, to compare the in vivo pharmacokinetics to their PEG-functionalized analogs. A series of five dSCKs was prepared from amphiphilic block copolymers, having different numbers and lengths of either PEG or PCB grafts, by supramolecular assembly in water followed by shell crosslinking, and then studied by a lactate assay to confirm their core hydrolytic degradabilities. Each dSCK was also conjugated with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) macrocyclic chelators and tyramine moieties to provide for 64Cu and/or radiohalogen labeling. The high specific activity of 64Cu radiolabeling ensured nanogram administration of dSCKs for in vivo evaluation of their pharmacokinetics. Biodistribution studies demonstrated comparable in vivo pharmacokinetic profiles of PCB-grafted dSCKs to their PEG-conjugated counterparts. These results indicated that PCB-functionalized dSCKs have great potential as a theranostic platform for translational research. PMID:23043240

  1. Fluorescent Cross-Linked Supramolecular Polymer Constructed by Orthogonal Self-Assembly of Metal-Ligand Coordination and Host-Guest Interaction.

    PubMed

    Qian, Xiaomin; Gong, Weitao; Li, Xiaopeng; Fang, Le; Kuang, Xiaojun; Ning, Guiling

    2016-05-10

    A new host molecule consists of four terpyridine groups as the binding sites with zinc(II) ion and a copillar[5]arene incorporated in the center as a spacer to interact with guest molecule was designed and synthesized. Due to the 120 ° angle of the rigid aromatic segment, a cross-linked dimeric hexagonal supramolecular polymer was therefore generated as the result of the orthogonal self-assembly of metal-ligand coordination and host-guest interaction. UV/Vis spectroscopy, (1) H NMR spectroscopy, viscosity and dynamic light-scattering techniques were employed to characterize and understand the cross-linking process with the introduction of zinc(II) ion and guest molecule. More importantly, well-defined morphology of the self-assembled supramolecular structure can be tuned by altering the adding sequence of the two components, that is, the zinc(II) ion and the guest molecule. In addition, introduction of a competitive ligand suggested the dynamic nature of the supramolecular structure. PMID:27062539

  2. Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

    PubMed

    Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap

    2015-08-26

    We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting. PMID:26258806

  3. A TIPS-TPDO-tetraCN-Based n-Type Organic Field-Effect Transistor with a Cross-linked PMMA Polymer Gate Dielectric.

    PubMed

    Jung, Sungyeop; Albariqi, Mohammed; Gruntz, Guillaume; Al-Hathal, Thamer; Peinado, Alba; Garcia-Caurel, Enric; Nicolas, Yohann; Toupance, Thierry; Bonnassieux, Yvan; Horowitz, Gilles

    2016-06-15

    Recent improvement in the performance of the n-type organic semiconductors as well as thin gate dielectrics based on cross-linked polymers offers new opportunities to develop high-performance low-voltage n-type OFETs suitable for organic complementary circuits. Using TIPS-tetracyanotriphenodioxazine (TIPS-TPDO-tetraCN) and cross-linked poly(methyl methacrylate) (c-PMMA), respectively as n-type organic semiconductor and gate dielectric, linear regime field-effect mobility (1.8 ± 0.2) × 10(-2) cm(2) V(-1)s(-1), small spatial standard deviation of threshold voltage (∼0.1 V), and operating voltage less than 3 V are attainable with the same device structure and contact materials used commonly for p-type OFETs. Through comparative static and dynamic characterizations of c-PMMA and PMMA gate dielectrics, it is shown that both smaller thickness and larger relative permittivity of c-PMMA contributes to reduced operating voltage. Furthermore, negligible hysteresis brings evidence to small trap states in the semiconductor near gate dielectric of the n-type OFETs with c-PMMA. The use of TIPS-TPDO-tetraCN and c-PMMA is fully compatible with polyethylene terephthalate substrate, giving promise to various flexible applications. PMID:27188403

  4. Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and copolymers made thereby

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1979-01-01

    Triazine compounds and cross-linked polymer compositions are made by heating aromatic nitriles to a temperature in the range of from about 100 C to about 700 C, and preferably in the range of from about 200 C to about 350 C, in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (1) organic sulfonic and sulfinic acids, (2) organic phosphonic and phosphinic acids, and (3)metallic acetylacetonates, at a pressure in the range of from about atmospheric pressure to about 10,000 psi and preferably in the range of from about 200 psi to about 750 psi. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers are made which are trimerized with or without a filler by the aforementioned catalytic trimerization process into triaryl-s-triazine ring containing or cross-linked polymeric or copolymeric products useful in applications requiring high thermal-oxidative stability and high performance structural properties at elevated temperatures.

  5. Generation of Pretilt Angle for Nematic Liquid Crystal Using the Photodimerization Method on Various New Photo-Crosslinkable Polyimide Based Polymers

    NASA Astrophysics Data System (ADS)

    Hwang, Jeoung-Yeon; Seo, Dae-Shik; Son, Jong-Ho; Suh, Dong Hack

    2001-07-01

    We synthesized the various new photo-crosslinkable polyimide based polymers and generation of pretilt angle for a nematic liquid crystal (NLC) using a photodimerization method on the photopolymers was studied. A good thermal stability of the photopolymers was measured by thermogravimatric analysis (TGA) measurement until 450°C. The NLC pretilt angle generated was about 2.5°-3.0° by polarized UV exposure on the photopolymers containing a biphenyl (BP), decyl (De), and cholesteryl(chol), chalcone(Chal) group, respectively. However, low pretilt angle of the NLC was measured by polarized UV exposure on the photopolymers containing the fluorine and chalcone group. The NLC pretilt angle generated is attributed to the biphenyl and alkyl moieties, and the photo-dimerized chalcone group of the photopolymer.

  6. Regulated dielectric loss of polymer composites from coating carbon nanotubes with a cross-linked silsesquioxane shell through free-radical polymerization.

    PubMed

    Sun, Da; Zhou, Zheng; Chen, Guang-Xin; Li, Qifang

    2014-11-12

    We report a synthetic strategy for coating multiwalled carbon nanotubes (MWCNTs) with cross-linked octa-methacrylate-polyhedral oligomeric silsesquioxane (MA-POSS) by direct, in situ free-radical polymerization in a controlled manner. This strategy resulted in a core-shell structure with an MWCNT center. The shell thickness could be varied from ∼ 7 nm to 40 nm by choosing different initiators, solvents, and weight ratios of MWCNT and octa-MA-POSS. Coated MWCNT hybrids had controlled electrical performance depending on the coating layer thickness and were well-dispersed in the polymer matrix. POSS-coated MWCNTs were compounded with poly(vinylidene fluoride) to obtain a composite with high dielectric permittivity and low dielectric loss. PMID:25337905

  7. Gelation of Copolymers Photo-crosslinked by Pendent Benzophenones

    NASA Astrophysics Data System (ADS)

    Christensen, Scott; Hayward, Ryan C.

    2012-02-01

    Copolymers containing pendent benzophenone (BP) groups provide a simple and powerful route to crosslinkable polymer films. While the solution state photo-chemistry of BP is well established, and crosslinking of polymers blended with BP has been studied in detail, the process of crosslinking by covalently attached BP has received comparatively little attention. We have prepared copolymers of BP with several different monomers, and studied gelation as a function of BP content and degree of photochemical conversion. Understanding the influence of polymer chemistry on crosslinking efficiency allows the appropriate choice of materials for nanostructured photo-crosslinkable polymer films and reactive polymer blends.

  8. Gelation of Copolymers Photo-crosslinked by Pendant Benzophenones

    NASA Astrophysics Data System (ADS)

    Christensen, Scott; Hayward, Ryan C.

    2011-03-01

    Copolymers containing pendant benzophenone (BP) groups provide a simple and powerful route to crosslinkable polymer films. While the solution state photo-chemistry of BP is well established, and crosslinking of polymers blended with BP has been studied in detail, the process of crosslinking by covalently attached BP has received comparatively little attention. We have prepared copolymers of BP with several different monomers, and studied gelation as a function of BP content and degree of photochemical conversion. We seek to understand the influence of polymer chemistry on crosslinking efficiency, to guide choices of materials for photo- crosslinkable polymer films and to provide a route for tailoring morphology in polymer blends.

  9. Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

    PubMed

    Zhang, Zhiyue; Maji, Samarendra; da Fonseca Antunes, André B; De Rycke, Riet; Hoogenboom, Richard; De Geest, Bruno G

    2016-06-13

    Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate. PMID:27142455

  10. High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature

    NASA Astrophysics Data System (ADS)

    Mindemark, Jonas; Sun, Bing; Törmä, Erik; Brandell, Daniel

    2015-12-01

    Incorporation of carbonate repeating units in a poly(ε-caprolactone) (PCL) backbone used as a host material in solid polymer electrolytes is found to not only suppress crystallinity in the polyester material, but also give higher ionic conductivity in a wide temperature range exceeding the melting point of PCL crystallites. Combined with high cation transference numbers, this electrolyte material has sufficient lithium transport properties to be used in battery cells that are operational at temperatures down to below 23 °C, thus clearly demonstrating the potential of using non-polyether electrolytes in high-performance all-solid lithium polymer batteries.

  11. Impact of in situ polymer coating on particle dispersion into solid laser-generated nanocomposites.

    PubMed

    Wagener, Philipp; Brandes, Gudrun; Schwenke, Andreas; Barcikowski, Stephan

    2011-03-21

    The crucial step in the production of solid nanocomposites is the uniform embedding of nanoparticles into the polymer matrix, since the colloidal properties or specific physical properties are very sensitive to particle dispersion within the nanocomposite. Therefore, we studied a laser-based generation method of a nanocomposite which enables us to control the agglomeration of nanoparticles and to increase the single particle dispersion within polyurethane. For this purpose, we ablated targets of silver and copper inside a polymer-doped solution of tetrahydrofuran by a picosecond laser (using a pulse energy of 125 μJ at 33.3 kHz repetition rate) and hardened the resulting colloids into solid polymers. Electron microscopy of these nanocomposites revealed that primary particle size, agglomerate size and particle dispersion strongly depend on concentration of the polyurethane added before laser ablation. 0.3 wt% polyurethane is the optimal polymer concentration to produce nanocomposites with improved particle dispersion and adequate productivity. Lower polyurethane concentration results in agglomeration whereas higher concentration reduces the production rate significantly. The following evaporation step did not change the distribution of the nanocomposite inside the polyurethane matrix. Hence, the in situ coating of nanoparticles with polyurethane during laser ablation enables simple integration into the structural analogue polymer matrix without additives. Furthermore, it was possible to injection mold these in situ-stabilized nanocomposites without affecting particle dispersion. This clarifies that sufficient in situ stabilization during laser ablation in polymer solution is able to prevent agglomeration even in a hot polymer melt. PMID:21298127

  12. Poly(ethyleneimine) cross-linked multilayers deposited onto solid surfaces and enzyme immobilization as a function of the film properties

    NASA Astrophysics Data System (ADS)

    Bucatariu, Florin; Ghiorghita, Claudiu-Augustin; Simon, Frank; Bellmann, Cornelia; Dragan, Ecaterina Stela

    2013-09-01

    Single polycation cross-linked multilayers, based on poly(ethyleneimine) (PEI), have been prepared using a method of 3,3‧,4,4‧-benzophenonetetracarboxylic-dianhydride (BTCDA)-mediated electrostatics and hydrogen bonds layer-by-layer assembly. Linear PEI [PEI(L)] and branched PEI [PEI(B)] were adsorbed from salt-free aqueous solutions, either onto silica microparticles with particle diameter of 40-60 μm (Daisogel type) and 9-11 μm (Davisil type) or silicon wafers. The BTCDA cross-linking of the polycation adsorbed onto the solid surface results in a surface covered with carboxylic groups. The cross-linked polycation layers, which are negatively charged over a wide range of pH, can adsorb a new positively charged polyelectrolyte layer. A regular increase of the single polycation multilayers onto silica microparticles was observed by zeta potential measurements and X-ray photoelectron spectroscopy. The immobilization of two enzymes (pepsin and lysozyme) onto the functionalized silica surface, via glutaraldehyde (GA), has been tested. The amount of the attached enzyme significantly depended on the isoelectric point of the enzyme. Surface characteristics, average height, ha, and average roughness, Ra, slightly increased after each modification step of the organic film.

  13. Automated direct-immersion solid-phase microextraction using crosslinked polymeric ionic liquid sorbent coatings for the determination of water pollutants by gas chromatography.

    PubMed

    Cordero-Vaca, María; Trujillo-Rodríguez, María J; Zhang, Cheng; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

    2015-06-01

    Four different crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were evaluated in an automated direct-immersion solid-phase microextraction method (automated DI-SPME) in combination with gas chromatography (GC). The crosslinked PIL coatings were based on vinyl-alkylimidazolium- (ViCnIm-) or vinylbenzyl-alkylimidazolium- (ViBzCnIm-) IL monomers, and di-(vinylimidazolium)dodecane ((ViIm)2C12-) or di-(vinylbenzylimidazolium)dodecane ((ViBzIm)2C12-) dicationic IL crosslinkers. In addition, a PIL-based hybrid coating containing multi-walled carbon nanotubes (MWCNTs) was also studied. The studied PIL coatings were covalently attached to derivatized nitinol wires and mounted onto the Supelco assembly to ensure automation when acting as SPME coatings. Their behavior was evaluated in the determination of a group of water pollutants, after proper optimization. A comparison was carried out with three common commercial SPME fibers. It was observed that those PILs containing a benzyl group in their structures, either in the IL monomer and crosslinker (PIL-1-1) or only in the crosslinker (PIL-0-1), were the most efficient sorbents for the selected analytes. The validation of the overall automated DI-SPME-GC-flame ionization detector (FID) method gave limits of detection down to 135 μg · L(-1) for p-cresol when using the PIL-1-1 and down to 270 μg · L(-1) when using the PIL-0-1; despite their coating thickness: ~2 and ~5 μm, respectively. Average relative recoveries with waters were of 85 ± 14 % and 87 ± 15 % for PIL-1-1 and PIL-0-1, respectively. Precision values as relative standard deviation were always lower than 4.9 and 7.6 % (spiked level between 10 and 750 μg · L(-1), as intra-day precision). Graphical Abstract Automated DI-SPME-GC-FID using crosslinked-PILs sorbent coatings for the determination of waterpollutants. PMID:25925853

  14. 'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film

    SciTech Connect

    Parthasarathy, Meera; Pillai, Vijayamohanan K. Mulla, Imtiaz S.; Shabab, Mohammed; Khan, M.I.

    2007-12-07

    Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe{sup 2+}-form of the entrapped protein is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.

  15. Examination of nanoformulated crosslinked polymers complexed with copper/zinc superoxide dismutase as a therapeutic strategy for angiotensin II-mediated hypertension

    NASA Astrophysics Data System (ADS)

    Savalia, Krupa

    Excessive generation of superoxide (O2·-) has been extensively implicated as a signaling molecule in cardiovascular pathologies, including hypertension. As a major risk factor for myocardial infarction, stroke, and heart failure, the morbidity and mortality associated with hypertension is a worldwide epidemic. Although there are several standard therapies that effectively lower blood pressure, many hypertensive patients have uncontrolled blood pressure despite taking available medications. Thus, there is a necessity to develop new pharmacotherapies that target novel molecular effectors (e.g. O2·-) that have been implicated to be integral in the pathogenesis of hypertension. To overcome the failed therapeutic impact of currently available antioxidants in cardiovascular disease, we developed a nanomedicine-based delivery system for the O2 ·- scavenging enzyme, copper/zinc superoxide dismutase (CuZnSOD), in which CuZnSOD protein is electrostatically bound to poly-L-lysine (PLL 50)-polyethylene glycol (PEG) block co-polymer to form CuZnSOD nanozyme. Different formulations of CuZnSOD nanozyme are covalently stabilized by either reducible or non-reducible crosslinked bonds between the PLL50-PEG polymers. Herein, we tested the overall hypothesis that PLL50-PEG CuZnSOD nanozyme delivers active CuZnSOD protein to neurons and decreases blood pressure in a model of Angll-dependent hypertension. As determined by electron paramagnetic resonance (EPR) spectroscopy, nanozymes retain full SOD enzymatic activity. Furthermore, non-reducible crosslinked nanozyme delivers active CuZnSOD protein to central neurons in culture (CATH.a neurons) without inducing significant neuronal toxicity. In vivo studies conducted in Angll-mediated hypertensive adult male C57BL/6 mice demonstrate that the non-reducible crosslinked nanozyme significantly attenuates blood pressure when given directly into the brain and prevents the further increase in hypertension when intravenously (IV) administered

  16. Persulfate initiated ultra-low cross-linked poly(N-isopropylacrylamide) microgels possess an unusual inverted cross-linking structure.

    PubMed

    Virtanen, O L J; Mourran, A; Pinard, P T; Richtering, W

    2016-05-01

    Cross-linking density and distribution are decisive for the mechanical and other properties of stimuli-sensitive poly(N-isopropylacrylamide) microgels. Here we investigate the structure of ultra-low cross-linked microgels by static light scattering and scanning force microscopy, and show that they have an inverted cross-linking structure with respect to conventional microgels, contrary to what has been assumed previously. The conventional microgels have the largest polymer volume fraction in the core from where the particle density decays radially outwards, whereas ultra-low cross-linked particles have the highest polymer volume fraction close to the surface. On a solid substrate these particles form buckled shapes at high surface coverage, as shown by scanning force micrographs. The special structure of ultra-low cross-linked microgels is attributed to cross-linking of the particle surface, which is exposed to hydrogen abstraction by radicals generated from persulfate initiators during and after polymerization. The particle core, which is less accessible to the diffusion of radicals, has consequently a lower polymer volume fraction in the swollen state. By systematic variation of the cross-linker concentration it is shown that the cross-linking contribution from peroxide under typical synthesis conditions is weaker than that from the use of 1 mol% N,N'-methylenebisacrylamide. Soft deformable hydrogel particles are of interest because they emulate biological tissues, and understanding the underlying synthesis principle enables tailoring the microgel structure for biomimetic applications. Deformability of microgels is usually controlled by the amount of added cross-linker; here we however highlight an alternative approach through structural softness. PMID:27033731

  17. Cross-linking and ultrathin grafted gradation of fluorinated polymers synthesized via initiated chemical vapor deposition to prevent surface reconstruction.

    PubMed

    Liu, Andong; Goktekin, Esma; Gleason, Karen K

    2014-12-01

    Poly(fluoroalkyl acrylate)s with long perfluorooctyl pendant groups have been found to lead to the release of biopersistent perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Those with no more than six perfluorinated carbons in pedant groups do not cause such problems. They, however, give poor dynamic water repellency due to extensive reorganization of surface fluorinated groups when exposed to the water interface. In this work, thin films exhibiting improved dynamic water repellency, as evidenced by water contact angle (WCA) measurements, were synthesized via substrate-independent initiated chemical vapor deposition (iCVD) from 1H,1H,2H,2H-perfluorooctyl acrylate (C6PFA) and divinylbenzene (DVB) using two methods: copolymerization and ultrathin grafted gradation. The copolymerization between C6PFA and the cross-linker, DVB, was confirmed by Fourier transform infrared (FTIR) spectroscopy. The cross-linking is concluded to hinder the reorganization of surface fluorinated groups. The grafted gradation, consisting of an ultrathin pC6PFA top layer and a pDVB base layer, was characterized by angle-resolved X-ray photoelectron spectroscopy (ARXPS) measurements, which indicated that the top layer of pC6PFA is <2.5 nm thick to achieve the best dynamic water repellency. The outmost surface of this structure is fully covered by fluorinated groups, giving hydrophobicity. Concurrently, thanks to the interlayer grafting and the ultrathinness of the top layer, the fluorinated groups' tendency to migrate away from water interface is sterically blocked by the highly cross-linked pDVB base layer. The proposed approaches effectively reduced WCA hysteresis of C6PFA-based thin film to as low as 26.9° while maintaining sufficient hydrophobicity (advanced WCA of 119.6°). Due to the conformal and substrate-independent nature of iCVD technique, the films could be used to coat textured surfaces to generate superhydrophobicity. PMID:25358035

  18. Love-Wave Biosensors Using Cross-Linked Polymer Waveguides on LiTaO{sub 3} Substrates

    SciTech Connect

    BENDER,FLORIAN; CERNOSEK,RICHARD W.; JOSSE,F.

    2000-07-13

    The design and performance of Love-wave sensors using cross-linked poly-(methyl methacrylate) waveguides of thickness of 0.3--3.2 {micro}m on LiTaO{sub 3} substrates are described. It is found that this layer-substrate combination provides sufficient waveguidance, and electrical isolation of the IDTs from the liquid environment to achieve low acoustic loss and distortion. In bio-sensing experiments, mass sensitivity up to 1,420 Hz/(ng/mm{sup 2}) is demonstrated.

  19. Porous polymers bearing functional quaternary ammonium salts as efficient solid catalysts for the fixation of CO2 into cyclic carbonates

    NASA Astrophysics Data System (ADS)

    Cai, Sheng; Zhu, Dongliang; Zou, Yan; Zhao, Jing

    2016-07-01

    A series of porous polymers bearing functional quaternary ammonium salts were solvothermally synthesized through the free radical copolymerization of divinylbenzene (DVB) and functionalized quaternary ammonium salts. The obtained polymers feature highly cross-linked matrices, large surface areas, and abundant halogen anions. These polymers were evaluated as heterogeneous catalysts for the synthesis of cyclic carbonates from epoxides and CO2 in the absence of co-catalysts and solvents. The results revealed that the synergistic effect between the functional hydroxyl groups and the halide anion Br- afforded excellent catalytic activity to cyclic carbonates. In addition, the catalyst can be easily recovered and reused for at least five cycles without significant loss in activity.

  20. Polymer-Solid Interface Connectivity and Adhesion: Design of a Pressure Sensitive Adhesive

    NASA Astrophysics Data System (ADS)

    Bunker, Shana P.; Wool, Richard P.

    2007-03-01

    Adhesion at polymer-solid interfaces was explored for a new bio-based PSA in terms of sticker groups φX on the polymer, receptor groups φY on the solid and the strength of the X-Y acid-base interaction, χ. The polymer-solid interface models of Gong, Lee and Wool were extended with new percolation models of entanglements and interface strength to determine the optimal sticker group concentration φ*X. For the general case where φY and χ are constant, it is predicted that when φX<φ*X, the peel strength behaves as G1c˜φX/φ*X and the locus of failure is adhesive between the polymer and the solid. However, when φX>φ*X, failure occurs cohesively in a polymer-polymer interface adjacent to the solid and the strength decreases as G1c˜φ*X/φX. The switch from adhesive to cohesive failure can be understood in terms of the changes in the chain conformations of the adhered chains and their decreasing interpenetration X with the bulk chains, via X˜1/r, where r = χφXφY. The optimal value of φX which maximizes the adhesion and determines the mode of failure is given by φ*X 0.07/C, and for typical values of the characteristic ratio C in the range 7-10, φ*X 1% mole fraction, corresponding to about 2 sticker groups per critical entanglement length Mc. Supported by USDA

  1. Polymer-encapsulated carbon capture liquids that tolerate precipitation of solids for increased capacity

    SciTech Connect

    Aines, Roger D; Bourcier, William L; Spadaccini, Christopher M; Stolaroff, Joshuah K

    2015-02-03

    A system for carbon dioxide capture from flue gas and other industrial gas sources utilizes microcapsules with very thin polymer shells. The contents of the microcapsules can be liquids or mixtures of liquids and solids. The microcapsules are exposed to the flue gas and other industrial gas and take up carbon dioxide from the flue gas and other industrial gas and eventual precipitate solids in the capsule.

  2. Continuous preparation of polymer coated drug crystals by solid hollow fiber membrane-based cooling crystallization.

    PubMed

    Chen, Dengyue; Singh, Dhananjay; Sirkar, Kamalesh K; Pfeffer, Robert

    2016-02-29

    A facile way to continuously coat drug crystals with a polymer is needed in controlled drug release. Conventional polymer coating methods have disadvantages: high energy consumption, low productivity, batch processing. A novel method for continuous polymer coating of drug crystals based on solid hollow fiber cooling crystallization (SHFCC) is introduced here. The drug acting as the host particle and the polymer for coating are Griseofulvin (GF) and Eudragit RL100, respectively. The polymer's cloud point temperature in its acetone solution was determined by UV spectrophotometry. An acetone solution of the polymer containing the drug in solution as well as undissolved drug crystals in suspension were pumped through the tube side of the SHFCC device; a cold liquid was circulated in the shell side to rapidly cool down the feed solution-suspension in the hollow-fiber lumen. The polymer precipitated from the solution and coated the suspended crystals due to rapid temperature reduction and heterogeneous nucleation; crystals formed from the solution were also coated by the polymer. Characterizations by scanning electron microscopy, thermogravimetric analysis, laser diffraction spectroscopy, X-ray diffraction, Raman spectroscopy, and dissolution tests show that a uniformly coated, free-flowing drug/product can be obtained under appropriate operating conditions without losing the drug's pharmaceutical properties and controlled release characteristics. PMID:26772536

  3. Cross-linked anion exchange membranes with pendent quaternary pyrrolidonium salts for alkaline polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lan, Chunhua; Fang, Jun; Guan, Yingjie; Zhou, Huili; Zhao, Jinbao

    2015-11-01

    Novel anion-exchange membranes based on two kinds of pyrrolidonium type ionic liquids, N-methyl-N-vinyl-pyrrolidonium (NVMP) and N-ethyl-N-vinyl-pyrrolidonium (NVEP), have been synthesized via polymerization and crosslinking treatment, followed by membrane casting. The covalent cross-linked structures of these membranes are confirmed by FT-IR. The obtained membranes are also characterized in terms of water uptake, ion exchange capacity (IEC), ionic conductivity as well as thermal, dimensional and chemical stability. The membranes display hydroxide conductivity of above 10-2 S cm-1 at 25 °C. Excellent thermal stability with onset degradation temperature above 235 °C, good alkaline stability in 6 mol L-1 NaOH at 60 °C for 168 h and remarkable dimensional stability of the resulting membranes have been proved. H2/air single fuel cells employed membrane M3 and N3 show the open-circuit voltage (OCV) of 0.953 V and 0.933 V, and the maximum power density of 88.90 mW cm-2 and 81.90 mW cm-2 at the current density of 175 mA cm-2 and 200 mA cm-2 at 65 °C, respectively.

  4. A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS.

    PubMed

    Zambrzycka, Elżbieta; Godlewska-Żyłkiewicz, Beata

    2014-01-01

    A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2'-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L(-1) aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL(-1). The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %. FigureThe new ion imprinted polymer was prepared and used for the separation of ruthenium from water and most complex environmental samples, such as road dust and platinum ore (CRM SARM 76) prior ETAAS determination. PMID:24966442

  5. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor); Dreyer, William J. (Inventor)

    1976-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree.C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  6. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1977-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree. C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  7. Preparation of porous polymer monolithic column using functionalized graphene oxide as a functional crosslinker for high performance liquid chromatography separation of small molecules.

    PubMed

    Li, Yaping; Qi, Li; Ma, Huimin

    2013-09-21

    A newly developed porous polymer monolith was prepared through copolymerization of 3-(trimethoxysilyl)propylmethacrylate modified graphene oxide with glycidyl methacrylate and ethylene dimethacrylate as a functional crosslinker, which was synthesized through silanization reaction of graphene oxide prepared by Hummers method with 3-(trimethoxysilyl)propylmethacrylate. The monolith was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, mercury intrusion porosimetry and nitrogen adsorption measurement. The monolith column was applied as the stationary phase of high performance liquid chromatography and its chromatographic performance was evaluated by separation of small molecules in the isocratic reversed-phase mode. The chromatograms of hydrophobic steroids and polar aromatic amines on the prepared monolith displayed the enhanced separation performance over those on the parent monolith. The reproducibility of the column was less than 3.5% in terms of relative standard deviation of retention time. The results demonstrate that copolymerization of functionalized graphene oxide into porous polymer monolith was an effective tool for chromatography separation enhancement of small molecules in an isocratic mode. PMID:23884304

  8. Polymers used to absorb fats and oils: A concept

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr.

    1974-01-01

    One approach to problem of excessive oils and fats is to develop method by which oil is absorbed into solid mixture for elimination as solid waste. Materials proposed for these purposes are cross-linked (network) polymers that have high affinity for aliphatic substances, i. e., petroleum, animal, and vegetable oils.

  9. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

  10. Solid mesostructured polymer-surfactant films at the air-liquid interface.

    PubMed

    Pegg, Jonathan C; Eastoe, Julian

    2015-08-01

    Pioneering work by Edler et al. has spawned a new sub-set of mesostructured materials. These are solid, self-supporting films comprising surfactant micelles encased within polymer hydrogel; composite polymer-surfactant films can be grown spontaneously at the air-liquid interface and have defined and controllable mesostructures. Addition of siliconalkoxide to polymer-surfactant mixtures allows for the growth of mesostructured hybrid polymer-surfactant silica films that retain film geometry after calcinations and exhibit superior mechanical properties to typically brittle inorganic films. Growing films at the air-liquid interface provides a rapid and simple means to prepare ordered solid inorganic films, and to date the only method for generating mesostructured films thick enough (up to several hundred microns) to be removed from the interface. Applications of these films could range from catalysis to encapsulation of hydrophobic species and drug delivery. Film properties and mesostructures are sensitive to surfactant structure, polymer properties and polymer-surfactant phase behaviour: herein it will be shown how film mesostructure can be tailored by directing these parameters, and some interesting analogies will be drawn with more familiar mesostructured silica materials. PMID:25127447

  11. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.

    PubMed

    Sun, Bing; Mindemark, Jonas; V Morozov, Evgeny; Costa, Luciano T; Bergman, Martin; Johansson, Patrik; Fang, Yuan; Furó, István; Brandell, Daniel

    2016-03-30

    Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments. PMID:26984668

  12. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    PubMed Central

    Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

  13. Investigation of solid polymer electrolyte gas sensor with different electrochemical techniques

    NASA Astrophysics Data System (ADS)

    Strzelczyk, A.; Jasinski, G.; Chachulski, B.

    2016-01-01

    In this work solid polymer electrolyte (SPE) amperometric sulphur dioxide sensor is investigated. Nafion was used as a membrane electrode and 1M sulphuric acid as an internal electrolyte. Sensor response to sulphur dioxide was measured. Besides traditional constant voltage amperometry also different electrochemical techniques were used. Results obtained by these methods are compared.

  14. Status of the development of solid polymer electrolyte water electrolysis for large scale hydrogen generation

    NASA Astrophysics Data System (ADS)

    Russell, J. H.

    1982-02-01

    Solid polymer electrolyte water electrolysis for large scale hydrogen generation is reported. The program was aimed at performance improvement. Reductions in cell impedance were demonstrated which improve cell performance by over 100 mV. A prototype 500 SCFH system for field evaluation was developed.

  15. An update of solid polymer electrolyte water electolysis programs at General Electric

    NASA Astrophysics Data System (ADS)

    Russell, J. H.

    At the previous two world hydrogen energy conferences in 1976 and 1978 the status of General Electric solid polymer electrolyte water electrolysis development program for large scale hydrogen generator was presented (Nuttall 1976, 1978). This paper updates the progress of this ongoing development program and also describes several new associated programs aimed at gaining early field experience on prototype systems.

  16. [Some aspects of water electrolysis with the use of a solid polymer electrolyte].

    PubMed

    Zorina, N G

    2006-01-01

    Electrochemical process in cells with a solid polymer electrolyte is dependent on catalyst durability in harsh environments and catalyst sputtering technology to ensure efficient power consumption. Active polymer electrolytes will permit to reduce substantially non-productive layouts and design a cost-effective, compact and safe system generator of high-purity oxygen and hydrogen. The existing designs of combined oxide systems integrating rear-earth and earth metals with a structure of Ln3+x Me2+1-x CoO3 containing perofskites were shown to be active catalysts in cells with a solid polymer electrolyte, and the sputtering technology was proven to reduce non-productive layouts in 2 or 2.5 times. PMID:17405280

  17. All-solid-state proton battery using gel polymer electrolyte

    SciTech Connect

    Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.

    2014-04-24

    A proton conducting gel polymer electrolyte system; PMMA+NH{sub 4}SCN+EC/PC, has been prepared. The highest ionic conductivity obtained from the system is 2.5 × 10−4 S cm{sup −1}. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO{sub 4}⋅7H{sub 2}O anode and MnO{sub 2} cathode. The open circuit voltage of the battery is 1.4 V and the highest energy density is 5.7 W h kg−1 for low current drain.

  18. Crosslinked Polyamide

    DOEpatents

    Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2002-06-04

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  19. Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates

    PubMed Central

    Saurer, Eric M.; Flessner, Ryan M.; Buck, Maren E.; Lynn, David M.

    2011-01-01

    We report on the fabrication of covalently crosslinked and amine-reactive hollow microcapsules using ‘reactive’ layer-by-layer assembly to deposit thin polymer films on sacrificial microparticle templates. Our approach is based on the alternating deposition of layers of a synthetic polyamine and a polymer containing reactive azlactone functionality. Multilayered films composed of branched poly(ethylene imine) (BPEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) were fabricated layer-by-layer on the surfaces of calcium carbonate and glass microparticle templates. After fabrication, these films contained residual azlactone functionality that was accessible for reaction with amine-containing molecules. Dissolution of the calcium carbonate or glass cores using aqueous ethylenediamine tetraacetic acid (EDTA) or hydrofluoric acid (HF), respectively, led to the formation of hollow polymer microcapsules. These microcapsules were robust enough to encapsulate and retain a model macromolecule (FITC-dextran) and were stable for at least 22 hours in high ionic strength environments, in low and high pH solutions, and in several common organic solvents. Significant differences in the behaviors of capsules fabricated on CaCO3 and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO3 templates collapsed upon drying, capsules fabricated on glass templates remained rigid and spherical. Characterization using EDS suggested that this latter behavior results, at least in part, from the presence of insoluble metal fluoride salts that are trapped or precipitate within the walls of capsules after etching of the glass cores using HF. Our results demonstrate that the assembly of BPEI/PVDMA films on sacrificial templates can be used to fabricate reactive microcapsules of potential use in a wide range of fields, including catalysis, drug and gene delivery, imaging, and

  20. Amorphous stabilization and dissolution enhancement of amorphous ternary solid dispersions: combination of polymers showing drug-polymer interaction for synergistic effects.

    PubMed

    Prasad, Dev; Chauhan, Harsh; Atef, Eman

    2014-11-01

    The purpose of this study was to understand the combined effect of two polymers showing drug-polymer interactions on amorphous stabilization and dissolution enhancement of indomethacin (IND) in amorphous ternary solid dispersions. The mechanism responsible for the enhanced stability and dissolution of IND in amorphous ternary systems was studied by exploring the miscibility and intermolecular interactions between IND and polymers through thermal and spectroscopic analysis. Eudragit E100 and PVP K90 at low concentrations (2.5%-40%, w/w) were used to prepare amorphous binary and ternary solid dispersions by solvent evaporation. Stability results showed that amorphous ternary solid dispersions have better stability compared with amorphous binary solid dispersions. The dissolution of IND from the ternary dispersion was substantially higher than the binary dispersions as well as amorphous drug. Melting point depression of physical mixtures reveals that the drug was miscible in both the polymers; however, greater miscibility was observed in ternary physical mixtures. The IR analysis confirmed intermolecular interactions between IND and individual polymers. These interactions were found to be intact in ternary systems. These results suggest that the combination of two polymers showing drug-polymer interaction offers synergistic enhancement in amorphous stability and dissolution in ternary solid dispersions. PMID:25196860

  1. In operando scanning electron microscopy and ultraviolet-visible spectroscopy studies of lithium/sulfur cells using all solid-state polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Marceau, Hugues; Kim, Chi-Su; Paolella, Andrea; Ladouceur, Sébastien; Lagacé, Marin; Chaker, Mohamed; Vijh, Ashok; Guerfi, Abdelbast; Julien, Christian M.; Mauger, Alain; Armand, Michel; Hovington, Pierre; Zaghib, Karim

    2016-07-01

    Lithium/solid polymer electrolyte (SPE)/sulfur cells were studied in operando by two techniques: Scanning Electron Microscope (SEM) and ultraviolet-visible absorption spectroscopy (UV-vis). During the operation of the cell, extensive polysulfide dissolution in the solid polymer electrolyte (cross-linked polyethylene oxide) leads to the formation of a catholyte. A clear micrograph of the thick passivation layer on the sulfur-rich anode and the decreased SPE thickness by cycling confirmed the failure mechanism; the capacity decays by reducing the amount of active material, and by contributing to a charge inhibiting mechanism called polysulfide shuttle. The formation of elemental sulfur is clearly visible in real time during the charge process beyond 2.3 V. The non-destructive in operando UV-vis study also shows the presence of characteristic absorption peaks evolving with cycling, demonstrating the accumulation of various polysulfide species, and the predominant formation of S42- and of S62- during discharge and charge, respectively. This finding implies that the charge and discharge reactions are not completely reversible and proceed along different pathways.

  2. Preparation of molecularly imprinted solid phase extraction using bensulfuron-methyl imprinted polymer and clean-up for the sulfonylurea-herbicides in soybean.

    PubMed

    Tang, Kaijie; Chen, Shangwei; Gu, Xiaohong; Wang, Haijun; Dai, Jun; Tang, Jian

    2008-04-28

    A pre-treatment methodology based on the molecularly imprinted solid phase extraction (MI-SPE) procedure was developed for the determination of bensulfuron-methyl (BSM), tribenuron-methyl (TBM), metsulfuron-methyl (MSM) and nicosulfuron (NS) in soybean samples. A molecular imprinted polymer (MIP) was prepared by precipitation polymerization using BSM as the template molecule, alpha-methacrylic acid (MAA) as the functional monomer, trimethylolpropane trimethacrylate (TRIM) as the cross-linker and dichloromethane as the porogen. The binding behaviors of the template BSM and its analogues on the MIP were evaluated by high performance liquid chromatography (HPLC). Then, solid phase extraction (SPE) with a BSM molecularly imprinted polymer (BSM-MIP) as adsorbent was investigated and the optimum loading, washing, and eluting conditions for MI-SPE of the selected BSM, MSM, TBM, and NS were established. The optimized MI-SPE procedure was used to extract the sulfonylureas and a high recovery was obtained in the soybean samples. PMID:18405688

  3. Quantification of the solid-state charge mobility in a model radical polymer

    SciTech Connect

    Baradwaj, Aditya G.; Rostro, Lizbeth; Boudouris, Bryan W.; Alam, Muhammad A.

    2014-05-26

    We establish that an oft-used radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), has a solid-state hole mobility value on the order of 10{sup −4} cm{sup 2} V{sup −1} s{sup −1} in a space charge-limited device geometry. Despite being completely amorphous and lacking any π-conjugation, these results demonstrate that the hole mobility of PTMA is comparable to many well-studied conjugated polymers [e.g., poly(3-hexylthiophene)]. Furthermore, we show that the space charge-limited charge carrier mobility of these macromolecules is only a weak function of temperature, in contrast to many thermally-activated models of charge transport in polymeric materials. This key result demonstrates that the charge transport in radical polymers is inherently different than that in semicrystalline, conjugated polymers. These results establish the mechanism of solid-state charge transport in radical polymers and provide macromolecular design principles for this emerging class of organic electronic materials.

  4. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    NASA Astrophysics Data System (ADS)

    Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

    2016-05-01

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10-1 - 10-3 Scm-1, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEOxNaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O+1 ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  5. The Production of Solid Dosage Forms from Non-Degradable Polymers.

    PubMed

    Major, Ian; Fuenmayor, Evert; McConville, Christopher

    2016-01-01

    Non-degradable polymers have an important function in medicine. Solid dosage forms for longer term implantation require to be constructed from materials that will not degrade or erode over time and also offer the utmost biocompatibility and biostability. This review details the three most important non-degradable polymers for the production of solid dosage forms - silicone elastomer, ethylene vinyl acetate and thermoplastic polyurethane. The hydrophobic, thermoset silicone elastomer is utilised in the production of a broad range of devices, from urinary catheter tubing for the prevention of biofilm to intravaginal rings used to prevent HIV transmission. Ethylene vinyl acetate, a hydrophobic thermoplastic, is the material of choice of two of the world's leading forms of contraception - Nuvaring® and Implanon®. Thermoplastic polyurethane has such a diverse range of building blocks that this one polymer can be hydrophilic or hydrophobic. Yet, in spite of this versatility, it is only now finding utility in commercialised drug delivery systems. Separately then one polymer has a unique ability that differentiates it from the others and can be applied in a specific drug delivery application; but collectively these polymers provide a rich palette of material and drug delivery options to empower formulation scientists in meeting even the most demanding of unmet clinical needs. Therefore, these polymers have had a long history in controlled release, from the very beginning even, and it is pertinent that this review examines briefly this history while also detailing the state-of-the-art academic studies and inventions exploiting these materials. The paper also outlines the different production methods required to manufacture these solid dosage forms as many of the processes are uncommon to the wider pharmaceutical industry. PMID:26898737

  6. Data Mining as a Guide for the Construction of Crosslinked Nanoparticles with Low Immunotoxicity via Controlling Polymer Chemistry and Supramolecular Assembly

    PubMed Central

    Elsabahy, Mahmoud; Wooley, Karen L.

    2015-01-01

    CONSPECTUS The potential immunotoxicity of nanoparticles that are currently being approved or in different phases of clinical trials or under rigorous in vitro and in vivo characterizations in several laboratories has recently raised special attention. Products with no apparent in vitro or in vivo toxicity may still trigger the various components of the immune system, unintentionally, and lead to serious adverse reactions. Cytokines are one of the useful biomarkers to predict the effect of biotherapeutics on modulating the immune system and for screening the immunotoxicity of nanoparticles, both in vitro and in vivo, and were found recently to partially predict the in vivo pharmacokinetics and biodistribution of nanomaterials. Control of polymer chemistry and supramolecular assembly provides a great opportunity for construction of biocompatible nanoparticles for biomedical clinical applications. However, the sources of data collected regarding immunotoxicities of nanomaterials are diverse and experiments are usually conducted using different assays and under specific conditions, making direct comparisons nearly impossible and, thus, tailoring properties of nanomaterials based on the available data is challenging. In this account, the effects of chemical structure, crosslinking, degradability, morphology, concentration and surface chemistry on the immunotoxicity of an expansive array of polymeric nanomaterials will be highlighted, with focus being given on assays conducted using the same in vitro and in vivo models and experimental conditions. Furthermore, numerical descriptive values have been utilized, uniquely, to stand for induction of cytokines by nanoparticles. This treatment of available data provides a simple and easy way to compare the immunotoxicity of various nanomaterials, and the values were found to correlate-well with published data. Based on the investigated polymeric systems in this study, valuable information has been collected that aids in the

  7. Solid phase extraction of food contaminants using molecular imprinted polymers.

    PubMed

    Baggiani, Claudio; Anfossi, Laura; Giovannoli, Cristina

    2007-05-15

    Food contamination from natural or anthropogenic sources poses severe risks to human health. It is now largely accepted that continuous exposure to low doses of toxic chemicals can be related to several chronic diseases, including some type of cancer and serious hormonal dysfunctions. Contemporary analytical methods have the sensitivity required for contamination detection and quantification, but direct application of these methods on food samples can be rarely performed. In fact, the matrix introduces severe disturbances, and analysis can be performed only after some clean-up and preconcentration steps. Current sample pre-treatment methods, mostly based on the solid phase extraction technique, are very fast and inexpensive but show a lack of selectivity, while methods based on immunoaffinity extraction are very selective but expensive and not suitable for harsh environments. Thus, inexpensive, rapid and selective clean-up methods, relaying on "intelligent" materials are needed. Recent years have seen a significant increase of the "molecularly imprinted solid phase extraction" (MISPE) technique in the food contaminant analysis. In fact, this technique seems to be particularly suitable for extractive applications where analyte selectivity in the presence of very complex and structured matrices represents the main problem. In this review, several applications of MISPE in food contamination analysis will be discussed, with particular emphasis on the extraction of pesticides, drugs residua, mycotoxins and environmental contaminants. PMID:17456421

  8. Enhanced electrical transport in ionic liquid dispersed TMAI-PEO solid polymer electrolyte

    SciTech Connect

    Gupta, Neha; Rathore, Munesh Dalvi, Anshuman; Kumar, Anil

    2014-04-24

    A polymer composite is prepared by dispersing ionic liquid [Bmim][BF{sub 4}] in Polyethylene oxide-tetra methyl ammonium iodide composite and subsequent microwave treatment. X-ray diffraction patterns confirm the composite nature. To explore possibility of proton conductivity in these films, electrical transport is studied by impedance spectroscopy and DC polarization. It is revealed that addition of ionic liquid in host TMAI-PEO solid polymer electrolyte enhances the conductivity by ∼ 2 orders of magnitude. Polarization measurements suggest that composites are essentially ion conducting in nature. The maximum ionic conductivity is found to be ∼2 × 10{sup −5} for 10 wt % ionic liquid.

  9. Solid polymer electrolytes derived from polyphenols. Final report, 28 April--27 October 1998

    SciTech Connect

    Filler, R.

    1998-11-09

    In the Phase-1 study, Tech Drive synthesized several phenol monomers. Two of these monomers, one of which is new, were converted to phenolic polymers by enzymatic means, using horseradish peroxidase and hydrogen peroxide. The monomers and polymers were fully characterize using thin layer chromatography, FT-IR and NMR spectroscopy, gel permeation chromatography and light scattering analyses. Solid polymeric electrolytes (SPEs) were formulated using the processable polyphenols. Ionic conductivity measurements of one of the SPEs based on a substituted polyphenol showed promising levels of ionic conductivity. Addition of a plasticizer dramatically improved the room temperature conductivity of the SPE film. Laboratory cells, fabricated using the SPEs, gave very promising results.

  10. 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.

  11. Wear resistance of the biocompatible phospholipid polymer-grafted highly cross-linked polyethylene liner against larger femoral head.

    PubMed

    Moro, Toru; Takatori, Yoshio; Kyomoto, Masayuki; Ishihara, Kazuhiko; Kawaguchi, Hiroshi; Hashimoto, Masami; Tanaka, Takeyuki; Oshima, Hirofumi; Tanaka, Sakae

    2015-07-01

    The use of larger femoral heads to prevent the dislocation of artificial hip joints has recently become more common. However, concerns about the subsequent use of thinner polyethylene liners and their effects on wear rate have arisen. Previously, we prepared and evaluated the biological and mechanical effects of a novel highly cross-linked polyethylene (CLPE) liner with a nanometer-scaled graft layer of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC). Our findings showed that the PMPC-grafted particles were biologically inert and caused no subsequent bone resorptive responses and that the PMPC-grafting markedly decreased wear in a hip joint simulator. However, the metal or ceramic femoral heads used in this previous study had a diameter of 26 mm. Here, we investigated the wear-resistance of the PMPC-grafted CLPE liner with a 40-mm femoral head during 10 × 10(6) cycles of loading in the hip joint simulator. The results provide preliminary evidence that the grafting markedly decreased gravimetric wear rate and the volume of wear particles, even when coupled with larger femoral heads. Thus, we believe the PMPC-grafting will prolong artificial hip joint longevity both by preventing aseptic loosening and by improving the stability of articular surface. PMID:25764495

  12. High voltage electric double layer capacitor using a novel solid-state polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sato, Takaya; Marukane, Shoko; Morinaga, Takashi; Kamijo, Toshio; Arafune, Hiroyuki; Tsujii, Yoshinobu

    2015-11-01

    We designed and fabricated a bipolar-type electric double layer capacitor (EDLC) with a maximum 7.5 V operating voltage using a new concept in solid electrolytes. A cell having a high operating voltage, that is free from liquid leakage and is non-flammable is achieved by a bipolar design utilizing a solid polymer electrolyte made up of particles in a three-dimensional array, such as crystals composed of 75 wt% of hybrid particles decorated with a concentrated ionic liquid polymer brush (PSiP) and 25wt% of an ionic liquid (IL). The resulting solid film had sufficient physical strength and a high enough ionic conductivity to function as an electrolyte. Solidification as well as ionic conduction is due to the regular array of PSiPs, thereby producing a high ion-conductivity from a networked path between cores containing an appropriate amount of IL as a plasticizer. The demonstration cell shows a relatively good cycle durability and rate properties up to a 10C discharge process. It also has a very small leakage current in continuous charging and better self-discharge properties, even at 60 °C, compared with conventional cells. This paper demonstrates the first successful fabrication of a bipolar EDLC in a simple structure using this novel polymer solid electrolyte.

  13. Exploiting methyl groups as motional labels for structure analysis in solid polymers.

    PubMed

    White, J L

    1997-12-01

    We report results of magic-angle spinning (MAS) nuclear Overhauser experiments on solid polymers. Specifically, the focus of this work is to demonstrate that methyl groups provide unique motional labels in crystalline and amorphous materials that may be exploited to provide spatial information. The motivation for this work stems from the fact that recently developed techniques for distance determination in organic solids, e.g. REDOR and related spin-echo methods, typically require isotopic labelling. Comparison of heteronuclear MAS 13C-1H NOE growth rates for bis-phenol A (a crystalline organic solid), polycarbonate, chloral polycarbonate, polystyrene, poly(4-methylstyrene), and poly(alpha-methylstyrene) confirms that methyl groups are the only sources of cross-relaxation in these rigid polymers. The experiments are straightforward, and have the advantage that no isotopic labelling is required. In general, decreased growth rates and increased induction periods for carbons distant from methyl groups are observed. Critical analysis of the data suggests that the rates are sensitive to packing density, and we address the contribution of intrachain and interchain interactions to the observed rates. We expect that methyl-stimulated NOE's are general to all rigid solids, and that these experiments could prove useful for local structure characterization of polymers in cases where isotopic labelling is not practical. PMID:9472795

  14. Influence of Unmodified and β-Glycerophosphate Cross-Linked Chitosan on Anti-Candida Activity of Clotrimazole in Semi-Solid Delivery Systems

    PubMed Central

    Szymańska, Emilia; Winnicka, Katarzyna; Wieczorek, Piotr; Sacha, Paweł Tomasz; Tryniszewska, Elżbieta Anna

    2014-01-01

    The combination of an antifungal agent and drug carrier with adjunctive antimicrobial properties represents novel strategy of complex therapy in pharmaceutical technology. The goal of this study was to investigate the unmodified and ion cross-linked chitosan’s influence on anti-Candida activity of clotrimazole used as a model drug in hydrogels. It was particularly crucial to explore whether the chitosans’ structure modification by β-glycerophosphate altered its antifungal properties. Antifungal studies (performed by plate diffusion method according to CLSI reference protocol) revealed that hydrogels obtained with chitosan/β-glycerophosphate displayed lower anti-Candida effect, probably as a result of weakened polycationic properties of chitosan in the presence of ion cross-linker. Designed chitosan hydrogels with clotrimazole were found to be more efficient against tested Candida strains and showed more favorable drug release profile compared to commercially available product. These observations indicate that novel chitosan formulations may be considered as promising semi-solid delivery system of clotrimazole. PMID:25272230

  15. Determination of polychlorinated biphenyls in ocean water and bovine milk using crosslinked polymeric ionic liquid sorbent coatings by solid-phase microextraction.

    PubMed

    Joshi, Manishkumar D; Ho, Tien D; Cole, William T S; Anderson, Jared L

    2014-01-01

    Crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were employed in the extraction of 21 polychlorinated biphenyls (PCBs) from ocean water and bovine milk using solid-phase microextraction (SPME). The extraction temperature, time, and concentration of sodium chloride added to the matrix were optimized in order to determine the best extraction conditions for the extraction of PCBs. The analytical performance of the crosslinked PIL-based SPME fibers was compared with a commercial 7 µm polydimethylsiloxane (PDMS) fiber using gas chromatography (GC) employing an electron capture detector (ECD) and mass spectrometric detection (MS). Higher sensitivities for PCBs were achieved using PIL-based fibers when compared to PDMS fiber due to the incorporation of benzyl moieties into the PIL structures. The limits of detection (LOD) for all PCBs were determined to be in the low ng L(-1) range using the three studied coatings. Recovery studies were performed for PCBs in ocean water and bovine milk to validate the applicability of the current SPME method. PMID:24274285

  16. Influence of unmodified and β-glycerophosphate cross-linked chitosan on anti-Candida activity of clotrimazole in semi-solid delivery systems.

    PubMed

    Szymańska, Emilia; Winnicka, Katarzyna; Wieczorek, Piotr; Sacha, Paweł Tomasz; Tryniszewska, Elżbieta Anna

    2014-01-01

    The combination of an antifungal agent and drug carrier with adjunctive antimicrobial properties represents novel strategy of complex therapy in pharmaceutical technology. The goal of this study was to investigate the unmodified and ion cross-linked chitosan's influence on anti-Candida activity of clotrimazole used as a model drug in hydrogels. It was particularly crucial to explore whether the chitosans' structure modification by β-glycerophosphate altered its antifungal properties. Antifungal studies (performed by plate diffusion method according to CLSI reference protocol) revealed that hydrogels obtained with chitosan/β-glycerophosphate displayed lower anti-Candida effect, probably as a result of weakened polycationic properties of chitosan in the presence of ion cross-linker. Designed chitosan hydrogels with clotrimazole were found to be more efficient against tested Candida strains and showed more favorable drug release profile compared to commercially available product. These observations indicate that novel chitosan formulations may be considered as promising semi-solid delivery system of clotrimazole. PMID:25272230

  17. Cross-Linked Nano-onions of Carbon Nitride in the Solid Phase: Existence of a Novel C48N12 Aza-Fullerene

    NASA Astrophysics Data System (ADS)

    Hultman, Lars; Stafström, Sven; Czigány, Zsolt; Neidhardt, Jörg; Hellgren, Niklas; Brunell, Ian F.; Suenaga, Kazu; Colliex, Christian

    2001-11-01

    We report a new fullerenelike material consisting of cross-linked nano-onions of C and N. Growth of the onion shells takes place atom by atom on a substrate surface and yields thin solid films during magnetron sputter deposition. Electron microscopy and energy loss spectroscopy show that the core shell contains up to 20 at. % N corresponding to C48N12 aza-fullerene composition. Nanoindentation of this nanostructured material gives high resilience with hardness 7 GPa, Young's modulus 37 GPa, and complete elastic recovery after loading with 0.5 mN to a depth of 75 nm. Total energy calculations show the stability of C60-2nN2n aza-fullerenes and suggest the existence of a novel C48N12 molecule.

  18. Second order multivariate curve resolution of Fourier transform infrared spectroscopic data of the photo-induced crosslinking of thymine functionalized polymers.

    PubMed

    Bortolato, Santiago A; McDonough, Kristin; Gurney, Richard W; Martino, Débora M

    2014-09-01

    A meaningful characterization of the photo-induced curing process of materials based on styrene monomers functionalized with thymine and charged ionic groups was accomplished using FT-IR spectroscopy in combination with second-order multivariate calibration algorithms. The polymer composition as well as the irradiation dose effects on the photo-crosslinking of copolymer films was experimentally determined. Each FT-IR absorption spectra was decomposed into the contribution of individual species by means of chemometric algorithms. A second-order strategy involving a three-way array for each sample and analyzing all arrays simultaneously was used. Temperature and solvent frequently have a strong influence on the FT-IR peak producing shifts and trilinearity lost. A new methodology to properly pre-align the spectroscopic matrix data is used based on the decomposition of a three-way array via a suitably initialized and constrained PARAFAC model. The chemical reaction mechanism describing the underlying process in terms of identifiable steps was determined. Associated key parameters and equilibrium rate constants that characterize the interconversion and stability of diverse species were predicted. Additionally, it was possible to quantify all the species even in the presence of a non-calibrated compound. PMID:24913877

  19. Gold nanoparticle mediated designing of non-hydrolytic sol-gel cross-linked metformin imprinted polymer network: a theoretical and experimental study.

    PubMed

    Roy, Ekta; Patra, Santanu; Madhuri, Rashmi; Sharma, Prashant K

    2014-03-01

    A sensitive and selective electrochemical sensor based on molecularly imprinted polymers was developed for trace level detection of metformin-an antidiabetic drug. For the first time, we have applied non-hydrolytic sol-gel matrix as a cross-linking agent in the field of molecular imprinting. To create the sol-gel matrix and enhance the electro-conductivity of the proposed sensor citrate-capped gold nanoparticle were used. The morphologies and properties of the sensor were characterized by scanning electron microscopy, cyclic voltammetry, electron impedance spectroscopy, chronocoulometry and differential pulse voltammetry. Energy of the HOMO and LUMO orbitals and Mülliken's atomic charges of template molecule were also calculated using density functional theory utilizing B3LYP with 3-21G-basis set. The theoretical results allied to the diagnostic criteria of the cyclic voltammetry indicate that the metformin redox mechanism is associated to the irreversible oxidation process of metformin-imino-group to N-hydroxyimino-group. The results demonstrated that the prepared sensor had excellent selectivity and high sensitivity for metformin in the linear range from 0.02 to 80 ng ml(-1) with a detection limit of 0.005 ng ml(-1) (S/N=3). The sensor was also successfully employed to detect metformin in pharmaceutical sample. PMID:24468360

  20. Control of molecular rotor rotational frequencies in porous coordination polymers using a solid-solution approach.

    PubMed

    Inukai, Munehiro; Fukushima, Tomohiro; Hijikata, Yuh; Ogiwara, Naoki; Horike, Satoshi; Kitagawa, Susumu

    2015-09-30

    Rational design to control the dynamics of molecular rotors in crystalline solids is of interest because it offers advanced materials with precisely tuned functionality. Herein, we describe the control of the rotational frequency of rotors in flexible porous coordination polymers (PCPs) using a solid-solution approach. Solid-solutions of the flexible PCPs [{Zn(5-nitroisophthalate)x(5-methoxyisophthalate)1-x(deuterated 4,4'-bipyridyl)}(DMF·MeOH)]n allow continuous modulation of cell volume by changing the solid-solution ratio x. Variation of the isostructures provides continuous changes in the local environment around the molecular rotors (pyridyl rings of the 4,4'-bipyridyl group), leading to the control of the rotational frequency without the need to vary the temperature. PMID:26368067

  1. Composite polymer positive electrodes in solid-state lithium secondary batteries

    SciTech Connect

    Novak, P.; Inganas, O.; Bjorklund, R.

    1987-06-01

    The authors have developed composite polymer electrodes for use in all solid-state batteries in combination with Li. The composite is formed from water soluble polypyrrole which is combined with the solid polymer electrolyte polyethylene oxide. The composite electrode shows enhanced coulombic capacity as compared to an electrode composed only of the electroactive material, polypyrrole. Coulombic efficiency is good (90-95%) and energy efficiency is acceptable (80-85%) in galvanostatic studies. Charge retention is rather poor due to self-discharge. They have obtained proof that the electroactivity is due to polypyrrole, through the use of in situ spectroelectrochemical studies. They have characterized the composite electrode using scanning electron microscopy and conductive measurements.

  2. Ambient-temperature, rechargeable, all-solid lithium/polypyrrole polymer battery

    SciTech Connect

    Kakuda, Satoko; Momma, Toshiyuki; Osaka, Tetsuya . Dept. of Applied Chemistry); Appetecchi, G.B.; Scrosati, B. . Dipt. di Chimica)

    1995-01-01

    An ambient-temperature, all-solid lithium battery was fabricated by combining a poly(acrylonitrile), PAN-based polymer electrolyte with a lithium metal anode and a polypyrrole, PPy, film cathode. The influence of the morphology of the PPy film cathode on the battery performance was investigated. The results show that the electrode morphology does not considerably influence the charge-discharge cycling response and that the solid-state, Li/PPy battery exhibits high coulombic efficiency, approaching 90%. However, at the present time, the battery has a poor shelf life, and work is in progress for overcoming this drawback.

  3. The NASA "PERS" Program: Solid Polymer Electrolyte Development for Advanced Lithium-Based Batteries

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.; Bennett, William R.

    2007-01-01

    In fiscal year 2000, The National Aeronautics and Space Administration (NASA) and the Air Force Research Laboratory (AFRL) established a collaborative effort to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The ultimate objective of this development program, which was referred to as the Polymer Energy Rechargeable System (PERS), was to establish a world-class technology capability and U.S. leadership in polymer-based battery technology for aerospace applications. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. Out of a total of 38 proposals received in response to a NASA Research Announcement (NRA) solicitation, 18 proposals (13 contracts and 5 grants) were selected for initial award to address these technical challenges. Brief summaries of technical approaches, results and accomplishments of the PERS Program development efforts are presented. With Agency support provided through FY 2004, the PERS Program efforts were concluded in 2005, as internal reorganizations and funding cuts resulted in shifting programmatic priorities within NASA. Technically, the PERS Program participants explored, to various degrees over the lifetime of the formal program, a variety of conceptual approaches for developing and demonstrating performance of a viable advanced solid polymer electrolyte possessing the desired attributes, as well as several participants addressing all components of an integrated cell configuration. Programmatically, the NASA PERS Program was very successful, even though the very challenging technical goals for achieving a viable solid polymer electrolyte material or

  4. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

    NASA Astrophysics Data System (ADS)

    Chandrahalim, Hengky; Fan, Xudong

    2015-12-01

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3‧-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3‧-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip.

  5. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10‑4 S cm‑1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  6. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

    PubMed Central

    Chandrahalim, Hengky; Fan, Xudong

    2015-01-01

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3′-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3′-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip. PMID:26674508

  7. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers.

    PubMed

    Chandrahalim, Hengky; Fan, Xudong

    2015-01-01

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3'-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3'-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm(2) per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm(2) per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip. PMID:26674508

  8. Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

  9. Solid polymer electrolyte (SPE) fuel cell technology program, phase 1/1A. [design and fabrication

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A solid polymer electrolyte fuel cell was studied for the purpose of improving the characteristics of the technology. Several facets were evaluated, namely: (1) reduced fuel cell costs; (2) reduced fuel cell weight; (3) improved fuel cell efficiency; and (4) increased systems compatibility. Demonstrated advances were incorporated into a full scale hardware design. A single cell unit was fabricated. A substantial degree of success was demonstrated.

  10. Stability of amorphous pharmaceutical solids: crystal growth mechanisms and effect of polymer additives.

    PubMed

    Sun, Ye; Zhu, Lei; Wu, Tian; Cai, Ting; Gunn, Erica M; Yu, Lian

    2012-09-01

    We review recent progress toward understanding and enhancing the stability of amorphous pharmaceutical solids against crystallization. As organic liquids are cooled to become glasses, fast modes of crystal growth can emerge. One such growth mode, the glass-to-crystal or GC mode, occurs in the bulk, and another exists at the free surface, both leading to crystal growth much faster than predicted by theories that assume diffusion defines the kinetic barrier of crystallization. These phenomena have received different explanations, and we propose that GC growth is a solid-state transformation enabled by local mobility in glasses and that fast surface crystal growth is facilitated by surface molecular mobility. In the second part, we review recent findings concerning the effect of polymer additives on crystallization in organic glasses. Low-concentration polymer additives can strongly inhibit crystal growth in the bulk of organic glasses, while having weaker effect on surface crystal growth. Ultra-thin polymer coatings can inhibit surface crystallization. Recent work has shown the importance of molecular weight for crystallization inhibitors of organic glasses, besides "direct intermolecular interactions" such as hydrogen bonding. Relative to polyvinylpyrrolidone, the VP dimer is far less effective in inhibiting crystal growth in amorphous nifedipine. Further work is suggested for better understanding of crystallization of amorphous organic solids and the prediction of their stability. PMID:22434258

  11. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

    NASA Astrophysics Data System (ADS)

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

    2015-12-01

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

  12. A molecularly imprinted polymer for the selective solid-phase extraction of dimethomorph from ginseng samples.

    PubMed

    Xu, Xuanwei; Liang, Shuang; Meng, Xinxin; Zhang, Min; Chen, Ying; Zhao, Dan; Li, Yueru

    2015-04-15

    A molecularly imprinted polymer (MIP) was synthesized and evaluated to selectively extract dimethomorph from ginseng samples. Dimethomorph molecularly imprinted polymers with template to monomer molar ratios were contrived and developed via precipitation polymerization employing methacrylic acid as functional monomer, ethylene dimethacrylate as cross-linker and butanone:N-heptane (7:3, v:v)as porogen. The LOD (limit of detection) of this method was 0.002 mg kg(-1), and the LOQ (limit of quantification) was 0.005 mg kg(-1). The different spiked level of ginseng was 0.1 mg kg(-1), 1.0 mg kg(-1), 5.0 mg kg(-1), and the average recovery of dimethomrph was 89.2-91.6%. Under the optimized condition, good linearity was obtained from 0.01 to 5 mg kg(-1) (r(2) ≥ 0.9997) with the relative standard deviations of less than 3.20%. This proposed MISPE-GC procedure eliminated the effect of template leakage on quantitative analysis and could be applied to direct determination of dimethomrph in ginseng samples. PMID:25795323

  13. Responsive Polymers End-Tethered in Solid-State Nanochannels: When Nanoconfinement Really Matters

    SciTech Connect

    Tagliazucchi, Mario; Azzaroni, Omar; Szleifer, Igal

    2010-09-08

    Solid state nanochannels modified with supramolecular architectures are a new and interesting class of stimuli-responsive nanofluidic element. Their fundamental understanding requires describing the behavior of soft-materials in confined geometries and its responses to changes in solution conditions. Here, a nanochannel modified with a polyelectrolyte brush is studied with a molecular theory that incorporates the conformational behavior of the polymers, electrostatic, van der Waals, and repulsive interactions coupled with the ability of the polymer segments to regulate their charge through acid-base equilibrium. The theory predicts pH-dependent ionic conductivity in excellent agreement with experimental observations. The polymer chains undergo large conformational changes triggered by variations in the outer solution environment and the conductivity of the device is shown to be controlled by the charge state of the polymer. The degree of polymer charge is largely affected by charge regulation and nanoconfinement effects. The molecular calculations show that the apparent pKa inside the pore departs from that in solution when increasing the curvature of the nanochannel.

  14. Tribological properties of polymer films and solid bodies in a vacuum environment

    NASA Technical Reports Server (NTRS)

    Fusaro, Robert L.

    1987-01-01

    The tribological properties of ten different polymer based materials were evaluated in a vacuum environment to determine their suitability for possible lubrication applications in a space environment, such as might be encountered on the proposed space station. A pin-on-disk tribometer was used and the polymer materials were evaluated either as solid body disks or as films applied to 440C HT stainless steel disks. A 440C HT stainless steel hemispherically tipped pin was slid against the polymer materials. For comparison, similar tests were conducted in a controlled air atmosphere of 50 percent relative humidity air. In most instances, the polymer materials lubricated much better under vacuum conditions than in air. Thus, several of the materials show promise as lubricants for vacuum applications. Friction coefficients of 0.05 or less and polymer material wear rates of up to 2 orders of magnitude less than in air were obtained. One material showed considerable promise as a traction drive material. Relatively high friction coefficients (0.36 to 0.52) and reasonably low wear rates were obtained in vacuum.

  15. Tribological properties of polymer films and solid bodies in a vacuum environment

    NASA Technical Reports Server (NTRS)

    Fusaro, Robert L.

    1988-01-01

    The tribological properties of ten different polymer based materials were evaluated in a vacuum environment to determine their suitability for possible lubrication applications in a space environment, such as might be encountered on the proposed Space Station. A pin-on-disk tribometer was used and the polymer materials were evaluated either as solid body disks or as films applied to 440C HT stainless steel disks. A 440C HT stainless steel hemispherically tipped pin was slid against the polymer materials. For comparison, similar tests were conducted in a controlled air atmosphere of 50 percent relative humidity air. In most instances, the polymer materials lubricated much better under vacuum conditions than in air. Thus, several of the materials show promise as lubricants for vacuum applications. Friction coefficients of 0.05 or less and polymer material wear rates of up to 2 orders of magnitude less than in air were obtained. One material showed considerable promise as a traction drive material. Relative high friction coefficients (0.36 to 0.52) and reasonably low wear rates were obtained in vacuum.

  16. Studies on the Properties of Plasticizer and Lithium Salt on PMMA-based Solid Polymer Electrolytes

    SciTech Connect

    Chew, K. W.; Tan, C. G.; Osman, Z.

    2010-03-11

    The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10{sup -10} Scm{sup -1} is obtained. This may be due to the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -1}. Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.

  17. Application of spherical silicate to prepare solid dispersion dosage forms with aqueous polymers.

    PubMed

    Nagane, Kentaro; Kimura, Susumu; Ukai, Koji; Takahashi, Chisato; Ogawa, Noriko; Yamamoto, Hiromitsu

    2015-09-30

    The objective of this study is to prepare and characterize solid dispersions of nifedipine (NP) using porous spherical silicate micro beads (MB) that were approximately 100 μm in diameter with vinylpyrrolidone/vinyl acetate copolymer (PVP/VA) and a Wurster-type fluidized bed granulator. Compared with previously reported solid dispersion using only MB, the supersaturation of NP dissolved from the proposed system of MB and PVP/VA was maintained during dissolution tests. The proposed system produced a solid dispersion product coated on MB, and morphology was maintained after the coating process to prepare solid dispersion; therefore, the powder characteristics, such as flowability of the proposed solid dispersion product, was tremendously preferable to that of the conventional spray-dried solid dispersions of NP with PVP/VA, expecting to make the consequent manufacturing processes easy for development. Another advantage in the terms of manufacturing is its simple process to prepare solid dispersion by spraying the drug and polymer that were dissolved in an organic solvent onto a MB in a Wurster-type fluidized bed granulator, thus, simplifying the optimization and scale-up with ease. PMID:26200750

  18. Solvent-shift strategy to identify suitable polymers to inhibit humidity-induced solid-state crystallization of lacidipine amorphous solid dispersions.

    PubMed

    Sun, Mengchi; Wu, Chunnuan; Fu, Qiang; Di, Donghua; Kuang, Xiao; Wang, Chao; He, Zhonggui; Wang, Jian; Sun, Jin

    2016-04-30

    The solvent-shift strategy was used to identify appropriate polymers that inhibit humidity-induced solid-state crystallization of amorphous solid dispersions (ASDs). Lacidipine with the polymers, PVP-K30, HPMC-E5 or Soluplus, were combined to form amorphous solid dispersions prepared by solvent evaporation. The formulations were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier-transform infrared spectroscopy (FT-IR) and were subjected to in vitro dissolution testing. The moisture had a significant impact on the amount dissolved for the solid dispersions. Molecular docking studies established that hydrogen bonding was critical for the stabilization of the solid dispersions. The rank order of the binding energy of the drug-polymer association was Soluplus (-6.21kcal/mol)>HPMC-E5 (-3.21kcal/mol)>PVP-K30 (-2.31kcal/mol). PVP-K30 had the highest water uptake among the polymers, as did ASD system of lacidipine-PVP-K30 ASDs. In the Soluplus ASDs, with its strong drug-polymer interactions and low water uptake, moisture-induced solid-state crystallization was not observed. PMID:26869398

  19. Cross-linker dynamics determine the mechanical properties of actin gels.

    PubMed Central

    Wachsstock, D H; Schwarz, W H; Pollard, T D

    1994-01-01

    To evaluate the contributions of cross-linker dynamics and polymer deformation to the frequency-dependent stiffness of actin filament gels, we compared the rheological properties of actin gels with three types of cross-linkers: a weak one, Acanthamoeba alpha-actinin (dissociation rate constant 5.2 s-1, association rate constant 1.1 x 10(6) M-1 s-1); a strong one, chicken smooth muscle alpha-actinin (dissociation rate constant 0.66 s-1, association rate constant 1.20 x 10(6) M-1 s-1); and an extremely strong one, biotin/avidin (dissociation rate constant approximately zero). The biotin/avidin cross-linked gel, whose behavior is determined by polymer bending alone, behaves like a solid and shows no frequency dependence. The amoeba alpha-actinin cross-linked gel behaves like a viscoelastic fluid, and the frequency dependence of the stiffness can be explained by a mathematical model for dynamically cross-linked gels. The stiffness of the chicken alpha-actinin cross-linked gel is independent of frequency, and has viscoelastic properties intermediate between the two. The two alpha-actinins have similar association rate constants for binding to actin filaments, consistent with a diffusion-limited reaction. Rigid cross-links make the gel stiff, but make it elastic without the ability to deform permanently. Dynamically cross-linked actin filaments should allow the cell to react passively to various outside forces without any sort of signaling. Slower, signal-mediated pathways, such as severing filaments or changing the affinity of cross-linkers, could alter the nature of these passive reactions. PMID:8011912

  20. Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices

    NASA Astrophysics Data System (ADS)

    Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

    2016-07-01

    Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices.Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength

  1. Preparation and evaluation of solid-phase microextraction fiber based on molecularly imprinted polymers for trace analysis of tetracyclines in complicated samples.

    PubMed

    Hu, Xiaogang; Pan, Jialiang; Hu, Yuling; Huo, Yin; Li, Gongke

    2008-04-25

    Molecularly imprinted polymer (MIP) is widely used in many fields because of its characteristics of high selectivity, chemical stability and easy preparation. To enhance the selectivity and applicability of solid-phase microextraction (SPME), a novel MIP-coated SPME fiber was firstly prepared by multiple co-polymerization method with tetracycline as template. It could be coupled directly to high-performance liquid chromatography (HPLC) and used for trace analysis of tetracyclines (TCs) in complicated samples. The characteristics and application of the fibers were investigated. The electron microscope provided a crosslinked and porous surface, and the average thickness of the MIP coating was 19.5 microm. Compared with the non-imprinted polymer (NIP) coated fibers, the special selectivity to tetracycline and structure-similar oxytetracycline, doxycycline, chlortetracycline were discovered with the MIP-coated fibers. The adsorption and desorption of TCs with the MIP-coated fiber could be achieved quickly. A method for the fluorimetric determination of four TCs by the MIP-coated SPME coupled with HPLC was developed. The optimized extraction conditions such as extraction solvent, desorption solvent, and stirring speed were studied. Linear ranges for the four TCs were 5.00-200 microg/L and detection limits were within the range of 1.0-2.3 microg/L. The method was applied to simultaneous multi-residue analysis of four TCs in the spiked chicken feed, chicken muscle, and milk samples with the satisfactory recoveries. PMID:18325526

  2. Use of nafion as a solid polymer electrolyte for the electroreduction of tungsten (VI) fluoride

    SciTech Connect

    Bettelheim, A.; Raven, A.; Polak, M.; Ozer, D. )

    1992-01-01

    In this paper a new method is described in which WF{sub 6} is electroreduced in a solid-state cell configuration with a Nafion membrane serving as a solid polymer electrolyte. Cyclic voltammetry indicates a behavior similar to that of metallic tungsten for coatings obtained at dry conditions and similar to that of tungsten oxide species when water vapor is not totally expelled. Surface analysis using Auger electroscope and x-ray photoelectron spectroscopy shows that solid-state electro-reduction of WF{sub 6} in dry conditions yields coatings free of fluorine, which contain much less oxygen than electrodeposits obtained from aqueous solutions. However, due to possible oxidation and reduction reactions occurring before and during the surface-analysis process, it is not possible at this state to determine the exact content of metallic and oxide species in the deposits obtained by the present method.

  3. Crack detection and monitoring in viscoelastic solids using polymer optical fiber sensors

    NASA Astrophysics Data System (ADS)

    Chen, Tao; Li, Zhihong; Song, Xiaochun; Zhou, Yanming; Guo, Haiyan; Xie, Zhong

    2016-03-01

    Detecting and monitoring of crack in viscoelastic solids, as a result of large and time-dependent deformations, are of great importance but have not been carried out sufficiently well. In this paper, polymer optical fibers (POFs) are employed to detect and monitor cracks in viscoelastic solids subjected to tensile loading. The sensor system is developed based on the variation of light intensity within the POFs when the POF sensors are loaded. The sensors show good stability, cost-effective, and large enough strain range (60%). The results demonstrate that in addition to monitoring the strain state of viscoelastic solids, the POFs strain sensors can detect initial cracks and monitor cracks propagation up to ultimate failure.

  4. Nanoporous polymer electrolyte

    SciTech Connect

    Elliott, Brian; Nguyen, Vinh

    2012-04-24

    A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

  5. Conducting polymer actuator based on chemically deposited polypyrrole and polyurethane-based solid polymer electrolyte working in air

    NASA Astrophysics Data System (ADS)

    Choi, Hwa-Jeong; Song, Young-Min; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

    2009-02-01

    Conducting polymers (CPs), such as polypyrrole, polythiophene, and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation states. Thus, their films or coatings can be easily switched by the application of a small voltage and current to change their volume during electrochemical redox processes. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient conditions. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO4)2. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyol: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as an actuator. To find the proper thickness of the PPy coating layer for actuation, we measured the displacements of the actuators according to the thickness of the PPy coating layer. The displacement of all actuators is discussed in connection with the properties of the SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film being able to work in air.

  6. Tailoring the physical properties of homopolymers and polymer nanocomposites via solid-state processing

    NASA Astrophysics Data System (ADS)

    Pierre, Cynthia

    Numerous approaches can be used to modify polymer properties. In this thesis, it is demonstrated that an innovative, continuous, industrially scalable process called solid-state shear pulverization (SSSP) can be used to enhance polymer properties with and without the addition of nanofillers. The SSSP process employs a modified twin-screw extruder in which the barrel is cooled rather than heated, resulting in the polymer being processed at a temperature below its glass transition temperature, if the polymer is amorphous, or its melt transition temperature, if the polymer is semi-crystalline. The material processed via SSSP experiences high levels of shear and compressive stresses, resulting in many repeated fragmentation and fusion steps during pulverization, which can lead to mechanochemistry. This research provides the first in-depth study on the effect of SSSP processing on the molecular structure as well as physical properties of homopolymers. Rheological characterization has demonstrated an increase in the melt viscosity of pulverized poly(ethylene terephthalate) (PET), which can be ascribed to the in situ formation of lightly branched PET. Further evidence of branched PET is provided via a dramatic increase in the rate of crystallization of the pulverized samples. These results suggest that SSSP processing can enhance the reuse and recyclability of PET. While SSSP processing has dramatic effects on the structure of polyesters and consequently their properties, a mild effect is observed for polyolefins. This thesis also demonstrates via a combination of methods that the well-exfoliated state can be achieved via SSSP processing of various polymer nanocomposites, using as-received, unmodified fillers. For example, extensive comparisons are made concerning the thermal stability in air or nitrogen atmosphere of polypropylene (PP)/clay, PP/graphite, and PP/carbon nanotube (CNT) nanocomposites made by SSSP. These comparisons suggest that the mechanism by which CNTs

  7. Ester Cross-Link Profiling of the Cutin Polymer of Wild-Type and Cutin Synthase Tomato Mutants Highlights Different Mechanisms of Polymerization.

    PubMed

    Philippe, Glenn; Gaillard, Cédric; Petit, Johann; Geneix, Nathalie; Dalgalarrondo, Michèle; Bres, Cécile; Mauxion, Jean-Philippe; Franke, Rochus; Rothan, Christophe; Schreiber, Lukas; Marion, Didier; Bakan, Bénédicte

    2016-02-01

    Cuticle function is closely related to the structure of the cutin polymer. However, the structure and formation of this hydrophobic polyester of glycerol and hydroxy/epoxy fatty acids has not been fully resolved. An apoplastic GDSL-lipase known as CUTIN SYNTHASE1 (CUS1) is required for cutin deposition in tomato (Solanum lycopersicum) fruit exocarp. In vitro, CUS1 catalyzes the self-transesterification of 2-monoacylglycerol of 9(10),16-dihydroxyhexadecanoic acid, the major tomato cutin monomer. This reaction releases glycerol and leads to the formation of oligomers with the secondary hydroxyl group remaining nonesterified. To check this mechanism in planta, a benzyl etherification of nonesterified hydroxyl groups of glycerol and hydroxy fatty acids was performed within cutin. Remarkably, in addition to a significant decrease in cutin deposition, mid-chain hydroxyl esterification of the dihydroxyhexadecanoic acid was affected in tomato RNA interference and ethyl methanesulfonate-cus1 mutants. Furthermore, in these mutants, the esterification of both sn-1,3 and sn-2 positions of glycerol was impacted, and their cutin contained a higher molar glycerol-to-dihydroxyhexadecanoic acid ratio. Therefore, in planta, CUS1 can catalyze the esterification of both primary and secondary alcohol groups of cutin monomers, and another enzymatic or nonenzymatic mechanism of polymerization may coexist with CUS1-catalyzed polymerization. This mechanism is poorly efficient with secondary alcohol groups and produces polyesters with lower molecular size. Confocal Raman imaging of benzyl etherified cutins showed that the polymerization is heterogenous at the fruit surface. Finally, by comparing tomato mutants either affected or not in cutin polymerization, we concluded that the level of cutin cross-linking had no significant impact on water permeance. PMID:26676255

  8. Stimulus-responsiveness and methyl violet release behaviors of poly(NIPAAm-co-AA) hydrogels chemically crosslinked with β-cyclodextrin polymer bearing methacrylates.

    PubMed

    Zhao, Hui; Gao, Jun; Liu, Ruina; Zhao, Sanping

    2016-06-16

    To fabricate thermo- and pH-sensitive hydrogels functionalized with β-cyclodextrin (β-CD) moieties, β-CD polymer bearing methacrylate (CDP-g-GMA) used as a reactive and functional crosslinker was synthesized, and then copolymerized with N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) in aqueous solution via UV-initiated free radical polymerization. The stimulus-responsiveness of the resultant hydrogels has been carried out by measuring the swelling ratio at different temperatures and pH values. The results showed that the thermo- and pH-sensitivities of the produced hydrogels were significantly dependent on the compositions of the hydrogels, and the dual sensitivities exhibited good reversible process. The interior morphology observed by SEM exhibited that the pore size of the hydrogels could be tailored by pH of the local medium. Using a water-soluble cationic dye methyl violet (MV) as a model drug, MV loading and release profiles of the hydrogels as potential drug controlled release carriers were evaluated. The MV release rate from CD-functionalized hydrogels was much slower than that from the hydrogel without β-CDs at both pH 2.0 and pH 7.4. The release of MV from CD-functionalized hydrogels at pH 2.0 was faster than that at pH 7.4, the release kinetics of MV from the CD-functionalized hydrogels displayed a sustained release profile, and the release mechanism followed Fickian diffusion. PMID:27152631

  9. Data Mining as a Guide for the Construction of Cross-Linked Nanoparticles with Low Immunotoxicity via Control of Polymer Chemistry and Supramolecular Assembly.

    PubMed

    Elsabahy, Mahmoud; Wooley, Karen L

    2015-06-16

    The potential immunotoxicity of nanoparticles that are currently being approved, in different phases of clinical trials, or undergoing rigorous in vitro and in vivo characterizations in several laboratories has recently raised special attention. Products with no apparent in vitro or in vivo toxicity may still trigger various components of the immune system unintentionally and lead to serious adverse reactions. Cytokines are one of the useful biomarkers for predicting the effect of biotherapeutics on modulation of the immune system and for screening the immunotoxicity of nanoparticles both in vitro and in vivo, and they were recently found to partially predict the in vivo pharmacokinetics and biodistribution of nanomaterials. Control of polymer chemistry and supramolecular assembly provides a great opportunity for the construction of biocompatible nanoparticles for biomedical clinical applications. However, the sources of data collected regarding immunotoxicities of nanomaterials are diverse, and experiments are usually conducted using different assays under specific conditions. As a result, making direct comparisons nearly impossible, and thus, tailoring the properties of nanomaterials on the basis of the available data is challenging. In this Account, the effects of chemical structure, cross-linking, degradability, morphology, concentration, and surface chemistry on the immunotoxicity of an expansive array of polymeric nanomaterials will be highlighted, with a focus on assays conducted using the same in vitro and in vivo models and experimental conditions. Furthermore, numerical descriptive values have been utilized uniquely to stand for induction of cytokines by nanoparticles. This treatment of available data provides a simple way to compare the immunotoxicities of various nanomaterials, and the values were found to correlate well with published data. On the basis of the polymeric systems investigated in this study, valuable information has been collected that

  10. Development of andrographolide molecularly imprinted polymer for solid-phase extraction

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoying; Liu, Qingshan; Jiang, Yifan; Luo, Yongming

    2011-06-01

    A method employing molecularly imprinted polymer (MIP) as selective sorbent for solid-phase extraction (SPE) to pretreat samples was developed. The polymers were prepared by precipitation polymerization with andrographolide as template molecule. The structure of MIP was characterized and its static adsorption capacity was measured by the Scatchard equation. In comparison with C 18-SPE and non-imprinted polymer (NIP) SPE column, MIP-SPE column displays high selectivity and good affinity for andrographolide and dehydroandrographolide for extract of herb Andrographis paniculata ( Burm.f.) Nees (APN). MIP-SPE column capacity was 11.9 ± 0.6 μmol/g and 12.1 ± 0.5 μmol/g for andrographolide and dehydroandrographolide, respectively and was 2-3 times higher than that of other two columns. The precision and accuracy of the method developed were satisfactory with recoveries between 96.4% and 103.8% (RSD 3.1-4.3%, n = 5) and 96.0% and 104.2% (RSD 2.9-3.7%, n = 5) for andrographolide and dehydroandrographolide, respectively. Various real samples were employed to confirm the feasibility of method. This developed method demonstrates the potential of molecularly imprinted solid phase extraction for rapid, selective, and effective sample pretreatment.

  11. Porous polymers bearing functional quaternary ammonium salts as efficient solid catalysts for the fixation of CO2 into cyclic carbonates.

    PubMed

    Cai, Sheng; Zhu, Dongliang; Zou, Yan; Zhao, Jing

    2016-12-01

    A series of porous polymers bearing functional quaternary ammonium salts were solvothermally synthesized through the free radical copolymerization of divinylbenzene (DVB) and functionalized quaternary ammonium salts. The obtained polymers feature highly cross-linked matrices, large surface areas, and abundant halogen anions. These polymers were evaluated as heterogeneous catalysts for the synthesis of cyclic carbonates from epoxides and CO2 in the absence of co-catalysts and solvents. The results revealed that the synergistic effect between the functional hydroxyl groups and the halide anion Br(-) afforded excellent catalytic activity to cyclic carbonates. In addition, the catalyst can be easily recovered and reused for at least five cycles without significant loss in activity. PMID:27365001

  12. Effect of low energy oxygen ion beam irradiation on ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Manjunatha, H. Kumaraswamy, G. N.; Damle, R.

    2014-04-24

    Over the past three decades, solid polymer electrolytes (SPEs) have drawn significant attention of researchers due to their prospective commercial applications in high energy-density batteries, electrochemical sensors and super-capacitors. The optimum conductivity required for such applications is about 10{sup −2} – 10{sup −4} S/cm, which is hard to achieve in these systems. It is known that the increase in the concentration of salt in the host polymer results in a continuous increase in the ionic conductivity. However, there is a critical concentration of the salt beyond which the conductivity decreases due to formation of ion pairs with no net charge. In the present study, an attempt is made to identify the concentration at which ion pair formation occurs in PEO: RbBr. We have attempted to modify microstructure of the host polymer matrix by low energy ion (Oxygen ion, O{sup +1} with energy 100 keV) irradiation. Ionic conductivity measurements in these systems were carried out using Impedance Spectroscopy before and after irradiation to different fluencies of the oxygen ion. It is observed that the conductivity increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains. The study reveals the importance of ion irradiation as an effective tool to enhance conductivity in SPEs.

  13. Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices.

    PubMed

    Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

    2016-08-01

    Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices. PMID:27109426

  14. The Roles of Matrix Polymer Crystallinity and Hydroxyapatite Nanoparticles in Modulating Material Properties of Photo-crosslinked Composites and Bone Marrow Stromal Cell Responses

    PubMed Central

    Wang, Shanfeng; Kempen, Diederik H. R.; Yaszemski, Michael J.; Lu, Lichun

    2010-01-01

    Two poly(ε-caprolactone fumarate)s (PCLFs) with distinct physical properties have been employed to prepare nanocomposites with hydroxyapatite (HA) nanoparticles via photo-crosslinking. The two PCLFs are PCLF530 and PCLF2000, named after their precursor PCL diol molecular weight of 530 and 2000 g.mol-1, respectively. Crosslinked PCLF530 is amorphous while crosslinked PCLF2000 is semi-crystalline with a melting temperature (Tm) of ∼40 °C and a crystallinity of 40%. Consequently, the rheological and mechanical properties of crosslinked PCLF2000 are significantly greater than those of crosslinked PCLF530. Structural characterizations and physical properties of both series of crosslinked PCLF/HA nanocomposites with HA compositions of 0%, 5%, 10%, 20%, and 30% have been investigated. By adding HA nanoparticles, crosslinked PCLF530/HA nanocomposites demonstrate enhanced rheological and mechanical properties while the enhancement in compressive modulus is less prominent in crosslinked PCLF2000/HA nanocomposites. In vitro cell attachment and proliferation have been performed using rat bone marrow stromal cells (BMSCs) and correlated with the material properties. Cell attachment and proliferation on crosslinked PCLF530/HA nanocomposite disks have been enhanced strongly with increasing the HA composition. However, surface morphology and surface chemistry such as composition, hydrophilicity, and the capability of adsorbing protein cannot be used to interpret the cell responses on different samples. Instead, the role of surface stiffness in regulating cell responses can be supported by the correlation between the change in compressive modulus and BMSC proliferation on these two series of crosslinked PCLFs and PCLF/HA nanocomposites. PMID:19339048

  15. Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

    2016-05-01

    Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

  16. Holographic polymer-dispersed liquid crystal Bragg grating integrated inside a solid core photonic crystal fiber.

    PubMed

    Zito, Gianluigi; Pissadakis, Stavros

    2013-09-01

    A polymer/liquid crystal-based fiber Bragg grating (PLC-FBG) is fabricated with visible two-beam holography by photo-induced modulation of a prepolymer/liquid crystal solution infiltrated into the hollow channels of a solid core photonic crystal fiber (PCF). The fabrication process and effects related to the photonic bandgap guidance into the infiltrated PCF, and characterization of the PLC-FBG, are discussed. Experimental data presented here demonstrate that the liquid crystal inclusions of the PLC-FBG lead to high thermal and bending sensitivities. The microscopic behavior of the polymer/liquid crystal phase separation inside the PCF capillaries is examined using scanning electron microscopy, and is discussed further. PMID:23988927

  17. Solid-supported polymer bilayers formed by coil-coil block copolymers.

    PubMed

    Yang, Yan-Ling; Tsao, Heng-Kwong; Sheng, Yu-Jane

    2016-08-14

    The formation and physical properties of solid-supported polymer bilayers (SPBs) on an adhesive substrate have been explored by dissipative particle dynamics simulations. A SPB is developed by the adsorption of vesicles formed by diblock copolymers in a selective solvent. The adsorbed vesicle can remain intact or become ruptured into a SPB, depending on the interaction between solvophobic blocks and solvent and the interaction between solvophilic blocks and the substrate. The morphological phase diagram of adsorbed vesicles is acquired. The influence of polymer adhesion strength and solvophobicity on the geometrical and mechanical properties of a SPB is systematically studied as well. It is found that vesicular disruption is easily triggered for strong adhesion strength. Moreover, for strong adhesion strength and weak solvophobicity, the fluctuation of membrane height is impeded while the area of fluctuation is enhanced. PMID:27418114

  18. Force response of actively deformed polymer microdroplets: dependence on the solid/liquid boundary condition

    NASA Astrophysics Data System (ADS)

    Heppe, Jonas; McGraw, Joshua D.; Bennewitz, Roland; Jacobs, Karin

    2015-03-01

    In fluid dynamics, the solid/liquid boundary condition can play a major role in the flow behavior of a liquid. For example, in the dewetting of identical polymer films on weak slip or strong slip substrates, large qualitative and quantitative differences are observed. Therefore, when applying an external load to a liquid resting on such substrates, the measured reaction forces and the ensuing flow should also depend on the boundary condition. We present atomic force microscopy measurements in which the reaction force of a cantilever is measured as the tip pierces liquid polymer micron sized droplets and films. These indentations are done on substrates with tuned slip. Accessing the size, depth and rate dependence of the resulting force distance curves, we show an influence of the slip condition on the dissipated energy and adhesion.

  19. A solid-state NMR method to determine domain sizes in multi-component polymer formulations

    NASA Astrophysics Data System (ADS)

    Schlagnitweit, Judith; Tang, Mingxue; Baias, Maria; Richardson, Sara; Schantz, Staffan; Emsley, Lyndon

    2015-12-01

    Polymer domain sizes are related to many of the physical properties of polymers. Here we present a solid-state NMR experiment that is capable of measuring domain sizes in multi-component mixtures. The method combines selective excitation of carbon magnetization to isolate a specific component with proton spin diffusion to report on domain size. We demonstrate the method in the context of controlled release formulations, which represents one of today's challenges in pharmaceutical science. We show that we can measure domain sizes of interest in the different components of industrial pharmaceutical formulations at natural isotopic abundance containing various (modified) cellulose derivatives, such as microcrystalline cellulose matrixes that are film-coated with a mixture of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC).

  20. 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

  1. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

    NASA Technical Reports Server (NTRS)

    Savinell, R. F.; Fritts, S. D.

    1988-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  2. A hybrid gel-solid-state polymer electrolyte for long-life lithium oxygen batteries.

    PubMed

    Luo, Wen-Bin; Chou, Shu-Lei; Wang, Jia-Zhao; Kang, Yong-Mook; Zhai, Yu-Chun; Liu, Hua-Kun

    2015-05-14

    A hybrid gel-solid-state polymer electrolyte has been used as the separator and an electrolyte for lithium oxygen batteries. It can not only avoid electrolyte evaporation but also protect the lithium metal anode during reactions over long-term cycling. Due to its high ionic conductivity and low activation energy, excellent cycling performance is demonstrated, in which the terminal voltage is higher than 2.2 V after 140 cycles at 0.4 mA cm(-2), with a capacity of 1000 mA h g(composite)(-1). PMID:25874974

  3. Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

    NASA Astrophysics Data System (ADS)

    Cheng, Hua; Scott, Keith

    The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

  4. Photoinduced processes in solid polymer solutions of dyes in an interference field of laser radiation

    SciTech Connect

    Sizykh, A G; Tarakanova, E A

    1998-12-31

    An investigation was made of the relationships governing the photochemical mechanism of formation of light-induced gratings in solid polymer solutions of a dye with a high quantum yield of the triplet states. The combined analysis of the results of real and numerical experiments was made for a solution of eosin K in gelatin. The protonation rate constant of the dye was measured and the dependence of the diffraction efficiency on the duration of irradiation was explained taking diffusion of the dye into account. A method was proposed for determination of the duffusion coefficient in a spatially modified interference field of the laser radiation. The diffusion coefficients were found. (nonlinear optical phenomena)

  5. Polymer space-charge-limited transistor as a solid-state vacuum tube triode

    NASA Astrophysics Data System (ADS)

    Chao, Yu-Chiang; Ku, Ming-Che; Tsai, Wu-Wei; Zan, Hsiao-Wen; Meng, Hsin-Fei; Tsai, Hung-Kuo; Horng, Sheng-Fu

    2010-11-01

    We report the construction of a polymer space-charge-limited transistor (SCLT), a solid-state version of vacuum tube triode. The SCLT achieves a high on/off ratio of 3×105 at a low operation voltage of 1.5 V by using high quality insulators both above and below the grid base electrode. Applying a greater bias to the base increases the barrier potential, and turns off the channel current, without introducing a large parasitic leakage current. Simulation result verifies the influence of base bias on channel potential distribution. The output current density is 1.7 mA/cm2 with current gain greater than 1000.

  6. Properties of solid polymer electrolyte fluorocarbon film. [used in hydrogen/oxygen fuel cells

    NASA Technical Reports Server (NTRS)

    Alston, W. B.

    1973-01-01

    The ionic fluorocarbon film used as the solid polymer electrolyte in hydrogen/oxygen fuel cells was found to exhibit delamination failures. Polarized light microscopy of as-received film showed a lined region at the center of the film thickness. It is shown that these lines were not caused by incomplete saponification but probably resulted from the film extrusion process. The film lines could be removed by an annealing process. Chemical, physical, and tensile tests showed that annealing improved or sustained the water contents, spectral properties, thermo-oxidative stability, and tensile properties of the film. The resistivity of the film was significantly decreased by the annealing process.

  7. Development status of the General Electric solid polymer electrolyte water electrolysis technology

    NASA Astrophysics Data System (ADS)

    Nuttall, L. J.

    The solid polymer electrolyte used by the considered technology is a thin sheet (5 to 10 mil thickness) of a sulfonated fluoropolymer. It is a high strength plastic material which serves as the sole electrolyte, and also forms a rugged barrier between the hydrogen and oxygen chambers. The electrodes consist of a thin catalyst layer bonded to the surfaces of the plastic sheet. A description is presented of a 60-cell module, operating at the normal design point of 1000 amps per square foot. The module generates more than 2000 standard cubic feet per hour of hydrogen at a pressure of approximately 100 psig. Performance and cost projections are discussed.

  8. Development status of solid polymer electrolyte water electrolysis for large scale hydrogen generation

    NASA Astrophysics Data System (ADS)

    Russell, J. H.

    1981-03-01

    Solid polymer water electrolysis technology for large scale hydrogen generation is reviewed. A hydrogen generator module, capable of producing 2000 SCFH, was operated successfully for over 700 hours in the 200 kW system. Test results and further information are presented. Technology development was continued in support of improving both capital cost and conversion efficiency. Progress made in the development of the 10 sq ft active area cell included completion of the initial design, the beginning of fabrication development, and installation of new facilities for cell manufacture.

  9. Selective trace analysis of sulfonylurea herbicides in water and soil samples based on solid-phase extraction using a molecularly imprinted polymer.

    PubMed

    Zhu, Qing-Zhi; Degelmann, Petra; Niessner, Reinhard; Knopp, Dietmar

    2002-12-15

    A molecularly imprinted polymer (MIP) was synthesized using the herbicide metsulfuron-methyl (MSM) as a template, 2-(trifluoromethyl)acrylic acid as a functional monomer, divinylbenzene as a cross-linker, and dichloromethane as a porogen. This polymer was used as a solid-phase extraction material for the quantitative enrichment of five sulfonylureas (nicosulfuron, thifensulfuron-methyl, metsulfuron-methyl, sulfometuron-methyl, and chlorsulfuron) in natural water and soil samples and off-line coupled to a reversed-phase HPLC/diode array detection (HPLC/DAD). Washing solvent was optimized in terms of kind and volume for removing the matrix constituents nonspecifically adsorbed on the MIP. It has been shown that the nonspecific binding ability of the sulfonylureas to the polymer largely increased along with increasing the concentration of Ca2+ ions in the water sample, whereas complexation of divalent ions with EDTA eliminated this interference completely. The stability of MIP was tested by consecutive percolation of water sample, and it was shown that the performance of the MIP did not vary even after 200 enrichment and desorption cycles. Recoveries of the five sulfonylureas extracted from 1 L of tap water and surface water samples such as river water and rainwater at a 50 ng/L spike level were not lower than 96%. The recoveries of sulfonylureas extracted from 10-g soil sample at the 50 microg/kg level were in the range of 71-139%. Depending on the particular compound, the limit of detection varied from 2 to 14 ng/L in water and from 5 to 12 microg/kg in soil samples. The MIP was also compared with a commercially available C-18 column and an immunoaffinity support with encapsulated polyclonal anti-MSM antibodies in sol-gel glass. PMID:12521169

  10. Application of solid polymer electrolyte to lithium/polypyrrole secondary battery system

    SciTech Connect

    Osaka, Tetsuya; Momma, Toshiyuki; Nishimura, Ken; Kakuda, Satoko; Ishii, Takayuki . Dept. of Applied Chemistry)

    1994-08-01

    An all solid-state lithium/polypyrrole (PPy) battery using polyethylene oxide (PEO)-LiClO[sub 4] as a solid polymer electrolyte was assembled, and the effects of the morphology of the PPy film and the concentration of LiClO[sub 4] on battery performance were investigated. Optimum conditions for the redox properties of PPy films in PEO-LiClO[sub 4] at 80 C were obtained with an LiClO[sub 4] concentration of n = 8 [approximately] 20 (n=[EO]/[Li]) when using rough PPy film. A Li/PPy battery using PEO-LiClO[sub 4] with optimized conditions exhibited high coulombic efficiency, above 90% at 0.1 mA cm [sup [minus]2] at 80 C. Cyclability of 1,400 cycles with high coulombic efficiency was attained.

  11. Growth of fullerene-like carbon nitride thin solid films consisting of cross-linked nano-onions

    NASA Astrophysics Data System (ADS)

    Czigány, Zs.; Brunell, I. F.; Neidhardt, J.; Hultman, L.; Suenaga, K.

    2001-10-01

    Fullerene-like CNx (x≈0.12) thin solid films were deposited by reactive magnetron sputtering of graphite in a nitrogen and argon discharge on cleaved NaCl and Si(001) substrates at 450 °C. As-deposited films consist of 5 nm diam CNx nano-onions with shell sizes corresponding to Goldberg polyhedra determined by high-resolution transmission electron microscopy. Electron energy loss spectroscopy revealed that N incorporation is higher in the core of the onions than at the perimeter. N incorporation promotes pentagon formation and provides reactive sites for interlinks between shells of the onions. A model is proposed for the formation of CNx nano-onions by continuous surface nucleation and growth of hemispherical shells.

  12. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

    2016-02-01

    The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

  13. Cu(I) stabilizing crosslinked polyethyleneimine.

    PubMed

    Movahedi, Alireza; Lundin, Angelica; Kann, Nina; Nydén, Magnus; Moth-Poulsen, Kasper

    2015-07-28

    Polyethyleneimine (PEI) is known for its metal-coordinating properties and in its crosslinked form has applications in different areas ranging from drug delivery to waste water treatment and recovery of trace metals. With the aim to regulate the coordination environment of Cu(I) and Cu(II) ions in marine coatings, we have prepared a triazole cross-linking agent with 'soft' coordination that can crosslink PEI via indirect reductive amination. We have shown that this triazole crosslinker not only increases the Cu(II) absorption capacity of the crosslinked PEI in comparison to the traditionally used glutaraldehyde-crosslinked PEI (PEI-GA), but also allows the crosslinked polymer network to stabilize the Cu(I) oxidation state more effectively. The Cu(II) uptake and Cu(I) stabilization of the polymer have been determined by elemental analysis and UV-vis spectroscopy. It was found that the triazole-crosslinked polymer (PEI-TA) could coordinate up to 12 wt% of Cu(II) before and 6 wt% Cu(II) after imine reduction. PMID:26104912

  14. 2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

    NASA Astrophysics Data System (ADS)

    Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

    2016-08-01

    Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

  15. A Process for Semi-Solid Moulding of High Viscosity Thermoplastic Polymers

    NASA Astrophysics Data System (ADS)

    Frick, Achim; Rochman, Arif; Martin, Peter

    2011-05-01

    A new moulding process for manufacturing micro parts made from high viscosity polymers has been developed as a result of a feasibility study. The process basically involves compression moulding of a polymeric preform by heating it up to its semi-solid state, i.e. between its glass transition temperature and melting temperature. The apparatus is made up of three main parts: a forming device, a single cavity micro mould and an induction heating system. The processing technique was successfully tested in the manufacturing of 10 mm round discs with a flange and inner bore using high viscosity polymers such as polyphenylene sulfide (PPS), polyetheretherketone (PEEK), ultra-high molecular weight polyethylene (UHMW PE) and polytetrafluoroethylene (PTFE). In a further miniaturization study, U-shaped micro seals with an outer diameter up to 2.5 mm were also successfully manufactured from non-injection mouldable PTFE. Thus, the new process is a realistic alternative technique to the existing micro moulding processes with respect to its capability to process a huge variety of polymers, even ultra high viscosity materials and the possibility to create micro parts with non-uniform wall thickness distributions.

  16. Solid-state synthesis and mechanical unfolding of polymers of T4 lysozyme.

    PubMed

    Yang, G; Cecconi, C; Baase, W A; Vetter, I R; Breyer, W A; Haack, J A; Matthews, B W; Dahlquist, F W; Bustamante, C

    2000-01-01

    Recent advances in single molecule manipulation methods offer a novel approach to investigating the protein folding problem. These studies usually are done on molecules that are naturally organized as linear arrays of globular domains. To extend these techniques to study proteins that normally exist as monomers, we have developed a method of synthesizing polymers of protein molecules in the solid state. By introducing cysteines at locations where bacteriophage T4 lysozyme molecules contact each other in a crystal and taking advantage of the alignment provided by the lattice, we have obtained polymers of defined polarity up to 25 molecules long that retain enzymatic activity. These polymers then were manipulated mechanically by using a modified scanning force microscope to characterize the force-induced reversible unfolding of the individual lysozyme molecules. This approach should be general and adaptable to many other proteins with known crystal structures. For T4 lysozyme, the force required to unfold the monomers was 64 +/- 16 pN at the pulling speed used. Refolding occurred within 1 sec of relaxation with an efficiency close to 100%. Analysis of the force versus extension curves suggests that the mechanical unfolding transition follows a two-state model. The unfolding forces determined in 1 M guanidine hydrochloride indicate that in these conditions the activation barrier for unfolding is reduced by 2 kcal/mol. PMID:10618384

  17. Overcoming sustainability and energy challenges in polymer science via solid-state shear pulverization

    NASA Astrophysics Data System (ADS)

    Brunner, Philip

    Solid-state shear pulverization (SSSP) is an innovative, continuous, environmentally benign, and industrially scalable process used to make materials that cannot be made via conventional processing techniques, reduce material cost by eliminating processing steps, and/or produce materials with superior properties as a result of better break-up and dispersion of additives. The SSSP process employs a modified twin-screw extruder in which the barrels are cooled rather than heated. This allows for high shear and compressive forces on the material during operation, which results in repeated fragmentation and fusion steps in the solid state. Technologically, this thesis provides the first in-depth study of the concept of specific energy in SSSP and how this variable can be tailored to optimize the end-properties while lowering costs for processing homopolymer, blend, or polymer composite systems. Furthermore, this thesis demonstrates the successful injection molding of SSSP-processed materials. An 80/20 wt% polypropylene (PP) and microcrystalline cellulose composite was manufactured with SSSP and injection molded into a bottle cap. These caps showed major benefits over neat PP such as increased stiffness and reduction in oxygen permeability. Finally, a description is provided of how SSSP can be used as a one-step solid-state compounding process that can add color, UV stabilizers, anti-statics, and other processing aids to polymer and uniformly and effectively disperses them in the polymer while pulverizing to a fine powder for roto-molding. Scientifically, process-structure-property relationships are investigated in detail with several homopolymers. The SSSP process is used to disperse heterogeneous nucleation agents (naturally found in commercial pellets) in the polymer. This led to major structural changes such as an increase in crystallizability and crystallinity for poly(lactic acid) (PLA) and in rigid amorphous fraction (RAF) at constant crystallinity for Nylon 11

  18. Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Qin; Ardebili, Haleh

    2016-01-01

    The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

  19. Molecularly imprinted polymer as efficient sorbent of solid-phase extraction for determination of gonyautoxin 1,4 in seawater followed by high-performance liquid chromatography-fluorescence detection.

    PubMed

    Mei, Xiao-Qi; He, Xiu-Ping; Wang, Jiang-Tao

    2016-08-01

    A kind of new molecularly imprinted polymer (MIP) was synthesized by bulk polymerization using guanosine as dummy template molecule, α-methacrylic acid as functional monomer and ethylene glycol dimethyl acrylic ester as crosslinker. Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) showed that the MIP had homogenous and uniform-sized cavities. It was confirmed that the MIP had higher binding affinity and selectivity towards gonyautoxins 1,4 (GTX 1,4) than the non-imprinted polymer (NIP) according to the static equilibrium adsorption. An off-line molecularly imprinted solid-phase extraction (MISPE) method followed by high-performance liquid chromatography with fluorescence detection (HPLC-FLD) was established for the analysis of GTX 1,4. 0.1 mol/L acetic acid and 95:5 (v:v) methanol/water were optimized as the washing and elution solutions, respectively. The recoveries of spiked cultured seawater samples were satisfactory, as high as 88 %. Using this method, the concentrations of GTX 1,4 from cultured seawater samples of Alexandrium minutum and Alexandrium tamarense were detected to be 1.10 μg/L and 0.99 μg/L, respectively. Graphical Abstract The synthesis of molecularly imprinted polymer and molecularly imprinted solid-phase extraction analysis for gonyautoxin 1,4. PMID:27317255

  20. Synthesis and characterization of molecularly imprinted polymer nanoparticles for coenzyme Q10 dispersive micro solid phase extraction.

    PubMed

    Contin, Mario; Bonelli, Pablo; Lucangioli, Silvia; Cukierman, Ana; Tripodi, Valeria

    2016-07-22

    Molecularly imprinted polymer nanoparticles (MIPNPs) with the ability to recognize coenzyme Q10 (CoQ10) were synthesised in order to be employed as sorbent in a dispersive micro-solid phase extraction (DMSPE) for the determination of CoQ10 in a liver extract. CoQ10 is a redox-active, lipophilic substance integrated in the mitochondrial respiratory chain which acts as an electron carrier, shuttling electrons from complex I (NADH-ubiquinone oxidoreductase) and II (succinate-ubiquinone oxidoreductase) to complex III (ubiquinol-cytochrome c reductase), for the production of cellular energy. The MIPNPs were synthesised by precipitation polymerization using coenzyme Q0 as the dummy template, methacrylic acid as the functional monomer, an acetonitrile: water mixture as the porogen, ethylene glycol dimethacrylate as the crosslinker and potassium persulfate as initiator. The nanoparticles were characterized by microscopy, capillary electrophoresis, dynamic light scattering, N2 adsorption-desorption isotherms, and infrared spectroscopy. The MIPNPs demonstrated the presence of selective cavities complementary to the quinone nucleus of CoQ10, leading to a specific recognition of CoQ10 compared with related compounds. In the liver extract the relative CoQ10 peak area (CoQ10 area/total peak area) increased from 4.6% to 25.4% after the DMSPE procedure. The recovery percentage of CoQ10 from the liver matrix was between 70.5% and 83.7% quantified against CoQ10 standard processed under the same conditions. The DMSPE procedure allows the elution of almost all the CoQ10 retained (99.4%) in a small volume (200μL), allowing the sample to be concentrated 2.5 times (LOD: 1.1μgg(-1) and LOQ: 3.7μgg(-1) of tissue). The resulted clean up of the sample, the improvement in peak shape and baseline and the reduction of interferences, evidence that the MIPNPs could potentially be applied as sorbent in a DMSPE with satisfactory results and with a minimum amount of sorbent (1mg). PMID:27317007

  1. A poly(phenyleneethynylene) polymer bearing amino acid substituents as active layer in enantioselective solid-state sensors

    NASA Astrophysics Data System (ADS)

    Tanese, M. C.; Hassan Omar, O.; Torsi, L.; Marinelli, F.; Colangiuli, D.; Farinola, G. M.; Babudri, F.; Naso, F.; Sabbatini, L.; Zambonin, P. G.

    2006-04-01

    A poly(phenyleneethynylene) polymer bearing amino acid pendant groups is used as enantioselective active layer in solid-state sensing devices. The chiral analyte in the present study is menthol in both the natural (-) and synthetic (+) enantiomers. The polymer bearing amino acid chiral sites is demonstrated to interact more favorably with the natural menthol than the synthetic one in a quartz crystal microbalance revealing system. Promising perspectives are seen for the use of such polymers in chiral discriminating, chemically sensitive resistors or even transistors.

  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. Effect of Drag Reducing Polymer and Suspended Solid on the Rate of Diffusion Controlled Corrosion in 90° Copper Elbow

    NASA Astrophysics Data System (ADS)

    Fouad, Mohamed Ahmed; Zewail, Taghreed Mohamed; Amine, Nieven Kamal Abbes

    2016-06-01

    Rate of diffusion controlled corrosion in 90° Copper Elbow acidified dichromate has been investigated in relation to the following parameters: effect of solution velocity in the absence and presence of drag- reducing polymer on the rate of diffusion controlled corrosion, and effect of the presence of suspended solids on the rate of diffusion controlled corrosion. It was found that the presence of drag reducing polymer inhibited the rate of mass transfer, while the presence of suspended solid increased significantly the rate of mass transfer.

  4. The characteristics of spontaneously forming physically cross-linked hydrogels composed of two water-soluble phospholipid polymers for oral drug delivery carrier I: hydrogel dissolution and insulin release under neutral pH condition.

    PubMed

    Nam, Kwangwoo; Watanabe, Junji; Ishihara, Kazuhiko

    2004-11-01

    Hydrogels bearing a phospholipid polar group, 2-methacryloyloxyethyl phosphorylcholine (MPC), were prepared from two aqueous solutions of polymers, water-soluble poly[MPC-co-methacrylic acid (MA)] (PMA) and poly[MPC-co-n-butyl methacrylate (BMA)] (PMB). The hydrogel, which was formed by physical cross-linking spontaneously without any chemical reactions and/or any physical stimuli, showed a controllable insulin release through a pH change in the medium by changing the hydrogen bonds. In this study, the mechanical strength, erosion of the hydrogel caused by polymer dissociation, and the release of insulin were examined with attention to the following three parameters of the MPC polymer: molecular weight of the polymers, composition of PMA and PMB (PMA/PMB ratio), and polymer concentration inside the hydrogel. The hydrogel with the highest mechanical strength was obtained at a PMA/PMB ratio = 3/7 (v/v, by volume ratio) while the hydrogel with the slowest dissolution was obtained at a ratio of 5/5 (v/v). The release was in good match with the dissolution and followed anomalous transport for all, but the diffusion exponent n changed according to the PMA/PMB ratio. An increase in the polymer concentration inside the hydrogel caused an increase in the mechanical strength of the hydrogel. When the polymer concentration was more than 20 wt.%, the absorption of water under neutral pH condition (pH 6.8) was observed. The release of insulin was suppressed below 10% during the swelling process of the hydrogel under neutral pH condition, while release was accelerated during the erosion process of the hydrogel. The relationship between erosion of the hydrogel and the release of the insulin depended on the erosion process of the hydrogel but differed according to the PMA/PMB ratio. PMID:15489127

  5. Cross-linked polyvinyl alcohol and method of making same

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Sheibley, D. W.; Philipp, W. H. (Inventor)

    1981-01-01

    A film-forming polyvinyl alcohol polymer is mixed with a polyaldehyde-polysaccharide cross-linking agent having at least two monosaccharide units and a plurality of aldehyde groups per molecule, perferably an average of at least one aldehyde group per monosaccharide units. The cross-linking agent, such as a polydialdehyde starch, is used in an amount of about 2.5 to 20% of the theoretical amount required to cross-link all of the available hydroxyl groups of the polyvinyl alcohol polymer. Reaction between the polymer and cross-linking agent is effected in aqueous acidic solution to produce the cross-linked polymer. The polymer product has low electrical resistivity and other properties rendering it suitable for making separators for alkaline batteries.

  6. Chain Dynamics in Solid Polymers and Polymerizing Systems as Revealed by Broadband Dielectric Spectroscopy

    NASA Astrophysics Data System (ADS)

    Williams, Graham

    2008-08-01

    A number of techniques are used to study the chain-dynamics of solid polymers, including those of dielectric relaxation [1-4], dynamic mechanical thermal analysis (DMTA) [1, 5], multinuclear NMR relaxations [6], quasi-elastic dynamic light scattering [7] and neutron scattering [8] (QELS & QENS) and transient fluorescence depolarization (TFD) [9]. Each technique has its own particular probe of the dynamics in a material. e.g. dielectric relaxation gives information on the angular motions of molecular chain-dipoles (for dipole relaxation) and the translational motions of ions (for f-dependent electrical conduction); NMR relaxations relate to the angular motions of chemical bonds; QELS relates to fluctuations in local refractive index; QENS to the time-dependent van Hove correlation function (suitably-defined) for proton-containing groups; TFD to the angular motions of fluorescent groups in a chain. Due to its relevance to practical applications of materials, DMTA is pre-eminent among the many physical techniques applied to solid polymers, but interpretations of behaviour in terms of molecular properties remain difficult since the direct link between an applied macroscopic stress and the molecular response of polymer chains in a bulk material remains an unsolved problem. Of the above techniques, Broadband Dielectric Spectroscopy (BDS) offers several advantages. (a) Materials may be studied in the frequency range 10-6 to 1010 Hz, over wide ranges of temperature and applied pressure, using commercially-available instrumentation. (b) Since the electrical capacitance of a film is inversely proportional its thickness, free-standing and supported films may be studied down to nm-thicknesses, giving e.g. information on the behaviour of the dynamic Tg as sample thickness approaches molecular dimensions. (c) Theoretical interpretations of dielectric relaxation and a.c. conduction are well-established in terms of Fourier transforms of molecular time correlation functions (TCFs

  7. Superionic solid-state polymer electrolyte membrane for high temperature applications

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Cao, Jinwei

    2015-03-01

    Completely amorphous, flexible, solid-state polymer electrolyte membranes (ss-PEM) consisted of polyethylene glycol diacrylate /succinonitrile plasticizer (SCN)/lithium trifluorosulfonyl imide were fabricated via UV polymerization. The room temperature ionic conductivity of our ss-PEM is extremely high (i.e., 10-3S/cm), which is already in the superionic conductor range of inorganic and/or liquid electrolyte counterparts. Of particular interest is that our ss-PEM is thermally stable up to 140°C, which is superior to the liquid electrolyte counterpart that degrades above 80°C. The ss-PEM exhibits cyclic stability in both LiFePO4/Li and Li4Ti5O12 /Li half-cells up to 50 cycles tested. The trend of conductivity enhancement with temperature is reproducible in the repeated cycles, showing melting transitions of the SCN plastic crystals. In the compositions close to the solid (SCN plastic crystal)-liquid coexistence line, polymerization-induced crystallization occurs during photo-curing. The effect of solid-liquid segregation on ionic conductivity behavior is discussed. Supported by NSF-DMR 1161070.

  8. Compact Ozone Differential Absorption Lidar (DIAL) Transmitter Using Solid-State Dye Polymers

    NASA Technical Reports Server (NTRS)

    Jones, Alton L., Jr.; DeYoung, Russell J.; Elsayid-Ele, Hani

    2001-01-01

    A new potential DIAL laser transmitter is described that uses solid-state dye laser materials to make a simpler, more compact, lower mass laser system. Two solid-state dye laser materials were tested to evaluate their performance in a laser oscillator cavity end pumped by a pulsed Nd:YAG laser at 532 nm. The polymer host polymethyl-methacrylate was injected with a pyrromethene laser dye, PM 580, or PM 597. A narrowband laser oscillator cavity was constructed to produce visible wavelengths of 578 and 600 nm which were frequency doubled into the UV region (299 or 300 nm) by using a BBO crystal, resulting in a maximum energy of 11 mJ at a wavelength of 578 nm when pumped by the Nd:YAG laser at an energy of 100 mJ (532 nm). A maximum output energy of 378 microJ was achieved in the UV region at a wavelength of 289 nm but lasted only 2000 laser shots at a repetition rate of 10 Hz. The results are promising and show that a solid-state dye laser based ozone DIAL system is possible with improvements in the design of the laser transmitter.

  9. Evaluation of possible treatment of solid RAW, containing polymer, with high frequency heating application

    SciTech Connect

    Dmitriev, S.A.; Markovskiy, S.F.; Savkin, A.E.; Sobolev, I.A.

    1995-12-31

    The waste arising in Moscow and the Moscow region comes for conditioning and disposal to the Moscow SIA Radon. In the total volume of solid waste, a sufficient part belongs to polymer materials, in particular, filters from different materials: polyvinylchloride (PVC), polyester, perchlorovinyl (PCV) and so on. Pure polymeric wastes are burnt with another type of waste, while the part of PVC in the waste that is burnt does not exceed 5% to meet the requirements of the technological process for the incineration unit. The main part of the waste mentioned earlier is not treated by SIA Radon, but is sent directly for disposal. According to the statistics of the last 5 years this part of the total volume of solid waste constitutes from 15 to 25%. Incineration of solid r/a waste with PVC content leads to gas purification system corrosion, due to HCl production; and also to sufficient amount of secondary waste arising, due to the process of off-gas neutralization. The aim of this paper is the determination of possible methods of the before mentioned waste treatment for reduction of its volume and transform in to an inert form.

  10. Synthesis and characterization of the magnetic molecularly imprinted polymer nanoparticles using N, N-bis methacryloyl ethylenediamine as a new cross-linking agent for controlled release of meloxicam.

    PubMed

    Azodi-Deilami, Saman; Abdouss, Majid; Kordestani, Davood

    2014-03-01

    The novel magnetic molecularly imprinted polymers (MMIPs) had been synthesized using N,N-bis methacryloyl ethylenediamine as a cross-linker for the controlled release of meloxicam at a pH of 1.0 (simulated gastric fluid), at a pH of 6.8 (simulated intestinal fluid) and at a pH of 7.4 (simulated biological fluids). The MMIPs were prepared via precipitation polymerization, using Fe3O4 as a magnetic component, meloxicam as a template molecule, methacrylic acid (MAA) as a functional monomer and N,N-bis methacryloyl ethylenediamine as a new cross-linker in acetonitrile/dimethyl sulfoxide porogen. Magnetic non-molecularly imprinted polymers (MNIPs) were also prepared with the same synthesis procedure as with MMIPs only without the presence of the template. The obtained MMIPs were characterized using transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR), dynamic light scattering (DLS), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and vibrating sample magnetometer (VSM). The performance of the MMIPs for the controlled release of meloxicam was assessed, and the results indicated that the magnetic MIPs also had potential applications in drug controlled release. PMID:24510441

  11. A (-)-norephedrine-based molecularly imprinted polymer for the solid-phase extraction of psychoactive phenylpropylamino alkaloids from Khat (Catha edulis Vahl. Endl.) chewing leaves.

    PubMed

    Atlabachew, Minaleshewa; Torto, Nelson; Chandravanshi, Bhagwan Singh; Redi-Abshiro, Mesfin; Chigome, Samuel; Mothibedi, Kediemetse; Combrinck, Sandra

    2016-07-01

    A molecularly imprinted polymer (MIP) was prepared using (-)-norephedrine as the template, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker and chloroform as the porogen. The MIP was used as a selective sorbent in the molecularly imprinted solid-phase extraction (MIP-SPE) of the psychoactive phenylpropylamino alkaloids, norephedrine and its analogs, cathinone and cathine, from Khat (Catha edulis Vahl. Endl.) leaf extracts prior to HPLC-DAD analysis. The MIP was able to selectively extract the alkaloids from the aqueous extracts of Khat. Loading, washing and elution of the alkaloids bound to the MIP were evaluated under different conditions. The clean baseline of the Khat extract obtained after MIP-SPE confirmed that a selective and efficient sample clean-up was achieved. Good recoveries (90.0-107%) and precision (RSDs 2.3-3.2%) were obtained in the validation of the MIP-SPE-HPLC procedure. The content of the three alkaloids in Khat samples determined after treatment with MIP-SPE and a commercial Isolute C18 (EC) SPE cartridge were in good agreement. These findings indicate that MIP-SPE is a reliable method that can be used for sample pre-treatment for the determination of Khat alkaloids in plant extracts or similar matrices and could be applicable in pharmaceutical, forensic and biomedical laboratories. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26531856

  12. Porous membrane-protected molecularly imprinted polymer micro-solid-phase extraction for analysis of urinary cocaine and its metabolites using liquid chromatography - Tandem mass spectrometry.

    PubMed

    Sánchez-González, Juan; Tabernero, María Jesús; Bermejo, Ana María; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

    2015-10-22

    Porous membrane-protected micro-solid phase extraction (μ-SPE) using a molecularly imprinted polymer (MIP) as an adsorbent has been proposed as an integrated extraction-cleanup procedure for isolating cocaine (COC) and its metabolites [benzoylecgonine (BZE), ecgonine methyl ester (EME), and cocaethylene (CE)] from human urine. MIP beads have been synthesized using COC as a template molecule, ethylene dimethacrylate (EDMA) as a functional monomer, divinylbenzene (DVB) as a cross-linker, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator. High performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS) has been used for quantifying the analytes after MIP-μ-SPE. Variables such as urine pH, adsorption temperature and time, mechanical (orbital-horizontal) stirring; and composition of the eluting solution and eluting time, were evaluated. The proposed method was shown to be precise and accurate [relative standard deviations (RSDs) of intra- and inter-day tests ranging from 3 to 8% and from 2 to 10%, respectively]; and analytical recoveries in the range of 89-100%). In addition, excellent accuracy was also verified after analyzing a FDT +25% control material for BZE. The detection limits were in the range of 0.16-1.7 ng L(-1), low enough for confirmative conclusions regarding cocaine abuse. The method was finally applied for screening/quantifying cocaine and metabolites in urine samples from poly-drug abusers. PMID:26526910

  13. Determination of ibuprofen, naproxen and diclofenac in aqueous samples using a multi-template molecularly imprinted polymer as selective adsorbent for solid-phase extraction.

    PubMed

    Madikizela, Lawrence Mzukisi; Chimuka, Luke

    2016-09-01

    This study describes the application of multi-template molecularly imprinted polymer (MIP) as selective sorbent in the solid-phase extraction (SPE) of naproxen, ibuprofen and diclofenac from wastewater and river water. MIP was synthesized at 70°C by employing naproxen, ibuprofen and diclofenac as multi-templates, ethylene glycol dimethacrylate, 2-vinyl pyridine and toluene as cross-linker, functional monomer and porogen, respectively. Wastewater and river water samples (pH 2.5) were percolated through SPE cartridge packed with 50mg of the MIP. The cartridge was washed with 2mL of methanol-water 10:90% (v:v) prior to elution with 2mL of acetic acid-acetonitrile 20:80% (v:v). Quantification of eluted compounds was performed with high performance liquid chromatography equipped with photo diode array detection. The detection limits were 0.15, 1.00 and 0.63μgL(-1) for naproxen, ibuprofen and diclofenac, respectively. Recoveries for naproxen, ibuprofen and diclofenac in deionized water spiked at 5 and 50μgL(-1) were greater than 80%. Ibuprofen was the most frequently detected compound with maximum concentrations of 221, 67.9 and 11.4μgL(-1) in wastewater influent, effluent and river water, respectively. PMID:27268945

  14. Playing with Polymers.

    ERIC Educational Resources Information Center

    Chemecology, 1997

    1997-01-01

    Presents an activity that enables students to gain a better understanding of the importance of polymers. Students perform an experiment in which polymer chains of polyvinyl acetate form crosslinks. Includes background information and discussion questions. (DDR)

  15. Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

    NASA Astrophysics Data System (ADS)

    Purohit, Parag

    Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification. Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used. It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone

  16. Rheology and structure of surface crosslinked surfactant-activated microgels.

    PubMed

    Li, Dongcui; Hsu, Raymond; Figura, Brian; Jacobs, Robert; Li, Sinan; Horvath, Steve; Clifford, Ted; Chari, Krishnan

    2016-09-14

    Nonionic surfactant-activated microgels (SAMs), composed of hydrophobic alkyl acrylates and hydrophilic hydroxyalkyl esters that utilize the effects of surfactant mediated swelling and interaction to provide pH-independent rheological properties, were previously reported as a new pathway to the rheology modification of surfactant solutions. Crosslinking was shown to play an important role in the properties of these soft microgel systems. To understand the impact of crosslinking chemistry on SAM polymers, we have compared two types of SAM polymers: a conventionally crosslinked SAM polymer via allyl pentaerythritol and a novel SAM polymer, where the surface is self-crosslinked via a reactive surfactant. We have systematically characterized the polymer's swelling, rheology and microstructure in a model system containing the polymer, sodium dodecyl sulfate (SDS) and water. Surface self-crosslinking is demonstrated to be a more effective crosslinking approach to create surfactant-mediated interactions between the microgel particles, resulting in more effective rheology modification. Internal crosslinking hinders both the full swelling of the SAM polymer as well as inter-particle bridging interactions, and is therefore less effective. To our best knowledge, this is the first report on creating a novel surface self-crosslinked microgel via a dual-functional reactive surfactant that interacts with a non-reactive surfactant to create a yield stress fluid. PMID:27470971

  17. Improving photo-stability of conjugated polymer MEH-PPV embedded in solid matrices by purification of the matrix polymer

    NASA Astrophysics Data System (ADS)

    Tian, Yuxi; Sheinin, Vladimir; Kulikova, Olga; Mamardashvili, Nugzar; Scheblykin, Ivan G.

    2014-04-01

    For single molecule spectroscopy (SMS), molecules under study are usually immobilized in a polymer matrix e.g. poly(methyl methacrylate). We show a very significant improvement of the conjugated polymer MEH-PPV photo-stability and decrease of the luminescence impurities concentration when the matrix is purified. We identify benzoyl peroxide (a common radical initiator) as a possible oxidizing agent which residuals in the polymer matrix destroy MEH-PPV. These results show that purification and selection of a matrix obtained by radical-free synthetic technique are of great importance for SMS as well as other technologies using polymer matrices as hosts for light-emitting materials.

  18. Development status of solid polymer electrolyte water electrolysis for manned spacecraft life support systems

    NASA Technical Reports Server (NTRS)

    Nuttall, L. J.; Titterington, W. A.

    1974-01-01

    Details of the design and system verification test results are presented for a six-man-rated oxygen generation system. The system configuration incorporates components and instrumentation for computer-controlled operation with automatic start-up/shutdown sequencing, fault detection and isolation, and with self-contained sensors and controls for automatic safe emergency shutdown. All fluid and electrical components, sensors, and electronic controls are designed to be easily maintainable under zero-gravity conditions. On-board component spares are utilized in the system concept to sustain long-term operation (six months minimum) in a manned spacecraft application. The system is centered on a 27-cell solid polymer electrolyte water electrolysis module which, combined with the associated system components and controls, forms a total system envelope 40 in. high, 40 in. wide, and 30 in. deep.

  19. Electrode assembly for use in a solid polymer electrolyte fuel cell

    DOEpatents

    Raistrick, Ian D.

    1989-01-01

    A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

  20. Solid polymer electrolyte water electrolysis system development. [to generate oxygen for manned space station applications

    NASA Technical Reports Server (NTRS)

    1975-01-01

    Solid polymer electrolyte technology used in a water electrolysis system (WES) to generate oxygen and hydrogen for manned space station applications was investigated. A four-man rated, low pressure breadboard water electrolysis system with the necessary instrumentation and controls was fabricated and tested. A six man rated, high pressure, high temperature, advanced preprototype WES was developed. This configuration included the design and development of an advanced water electrolysis module, capable of operation at 400 psig and 200 F, and a dynamic phase separator/pump in place of a passive phase separator design. Evaluation of this system demonstrated the goal of safe, unattended automated operation at high pressure and high temperature with an accumulated gas generation time of over 1000 hours.

  1. Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

    SciTech Connect

    Richardson, Thomas J.; Ross, Philip N.

    1999-01-01

    A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85.degree. C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1.times.10.sup.-8 cm.sup.2 /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

  2. Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

    SciTech Connect

    Richardson, T.J.; Ross, P.N.

    1999-12-21

    A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85 C or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1 {times} 10{sup {minus}8}cm{sup 2}/second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

  3. Corrosive characteristics of surface-modified stainless steel bipolar plate in solid polymer fuel cell

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaowen; Wang, Lixia; Sun, Juncai

    2015-03-01

    In this paper, corrosion behavior of an AISI 304 stainless steel modified by niobium or niobium nitride (denoted as niobized 304 SS and Nb-N 304 SS, respectively) is investigated in simulated solid polymer fuel cell (SPFC) operating conditions. Potentiodynamic polarizations show that the corrosion potentials of surface modified 304 SS shift to positive direction while the corrosion current densities decrease greatly comparing with the bare 304 SS in simulated anodic SPFC environments. The order of corrosive resistance in corrosive potential, corrosive current density and pitting potential is: Nb-N 304 SS > niobized 304 SS > bare 304 SS. In the methanol-fueled SPFC operating conditions, the results show that the corrosion resistance of bare and niobized 304 SS increases with the methanol concentration increasing in the test solutions.

  4. Solid-state sodium batteries using polymer electrolytes and sodium intercalation electrode materials

    SciTech Connect

    Ma, Y. |

    1996-08-01

    Solid-state sodium cells using polymer electrolytes (polyethylene oxide mixed with sodium trifluoromethanesulfonate: PEO{sub n}NaCF{sub 3}SO{sub 3}) and sodium cobalt oxide positive electrodes are characterized in terms of discharge and charge characteristics, rate capability, cycle life, and energy and power densities. The P2 phase Na{sub x}CoO{sub 2} can reversibly intercalate sodium in the range of x = 0.3 to 0.9, giving a theoretical specific energy of 440 Wh/kg and energy density of 1,600 Wh/l. Over one hundred cycles to 60% depth of discharge have been obtained at 0.5 mA/cm{sup 2}. Experiments show that the electrolyte/Na interface is stable and is not the limiting factor to cell cycle life. Na{sub 0.7}CoO{sub 2} composite electrodes containing various amounts of carbon black additive are investigated. The transport properties of polymer electrolytes are the critical factors for performance. These properties (the ionic conductivity, salt diffusion coefficient, and ion transference number) are measured for the PEO{sub n}NaCF{sub 3}SO{sub 3} system over a wide range of concentrations at 85 C. All the three transport properties are very salt-concentration dependent. The ionic conductivity exhibits a maximum at about n = 20. The transference number, diffusion coefficient, and thermodynamic factor all vary with salt concentration in a similar fashion, decreasing as the concentration increases, except for a local maximum. These results verify that polymer electrolytes cannot be treated as ideal solutions. The measured transport-property values are used to analyze and optimize the electrolytes by computer simulation and also cell testing. Salt precipitation is believed to be the rate limiting process for cells using highly concentrated solutions, as a result of lower values of these properties, while salt depletion is the limiting factor when a dilute solution is used.

  5. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    2013-11-01

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4'-diphenylmethane diisocyanate (2,4'-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF3SO3) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10-6 S cm-1 when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600-3100 cm-1, carbonyl (-C=O) at 1750-1650 cm-1 and ether (-C-O-C-) at 1150-1000 cm-1 of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF3SO3 salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF3SO3.

  6. Electrochemical redox properties of polypyrrole/Nafion composite film in a solid polymer electrolyte battery

    SciTech Connect

    Momma, Toshiyuki; Kakuda, Satoko; Yarimizu, Hideki; Osaka, Tetsuya

    1995-06-01

    Nafion{reg_sign} was introduced into a polypyrrole (PPy) matrix, and the redox performance of the PPy/Nafion electrode was investigated in a polyethylene oxide (PEO)-LiClO{sub 4} electrolyte. A rougher interface between polymer cathode and polymer electrolyte is usually needed for an all-solid battery, however, the PPy/Nafion cathode works well regardless of the flat surface of the PPy/Nafion film. When compared to a PPy film doped with ClO{sub 4}{sup {minus}} anions with a similar morphology, the PPy/Nafion film showed better redox performance. The results of the impedance spectroscopy and potential-step chronoamperometry confirmed that the improvement in the redox reaction of the PPy/Nafion film was due to the enhancement of the ion diffusion rate in the film. Thus, the PPy/Nafion film showed good charging-discharging properties in a rechargeable Li/PEO-LiClO{sub 4}/(PPy/Nafion) battery.

  7. Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

    NASA Astrophysics Data System (ADS)

    Praveen, D.; Damle, Ramakrishna

    2016-05-01

    Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO4)2, NH4I etc., have already been tried in the past with some success. Also various nanoparticles like Al2O3, TiO2 etc., have been tried in the past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.

  8. Molecularly imprinted polymer solid-phase extraction for detection of zearalenone in cereal sample extracts.

    PubMed

    Lucci, Paolo; Derrien, Delphine; Alix, Florent; Pérollier, Céline; Bayoudh, Sami

    2010-07-01

    The aim of this work was to develop a method for the clean-up and preconcentration of zearalenone from corn and wheat samples employing molecularly imprinted polymer (MIP) as selective sorbent for solid-phase extraction (SPE). Cereal samples were extracted with acetonitrile/water (75:25, v/v) and the extract was diluted with water and applied to an AFFINIMIP ZON MIP-SPE column. The column was then washed to eliminate the interferences and zearalenone was eluted with methanol and quantified using HPLC with fluorescence detection (lambda(exc)=275/lambda(em)=450 nm). The precision and accuracy of the method were satisfactory for both cereals at the different fortification levels tested and it gave recoveries between 82 and 87% (RSDr 2.5-6.2%, n=3) and 86 and 90% (RSDr 0.9-6.8%, n=3) for wheat and maize, respectively. MIP-SPE column capacity was determined to be not less than 6.6 microg of zearalenone and to be at least four times higher than that of immunoaffinity column (IAC). The application of AFFINIMIP ZON molecularly imprinted polymer as a selective sorbent material for detection of zearalenone fulfilled the method performance criteria required by the Commission Regulation (EC) No. 401/2006, demonstrating the suitability of the technique for the control of zearalenone in cereal samples. PMID:20579483

  9. Knitting aromatic polymers for efficient solid-phase microextraction of trace organic pollutants.

    PubMed

    Liu, Shuqin; Hu, Qingkun; Zheng, Juan; Xie, Lijun; Wei, Songbo; Jiang, Ruifen; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

    2016-06-10

    A series of knitting aromatic polymers (KAPs) were successfully synthesized using a simple one-step Friedel-Crafts alkylation of aromatic monomers and were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Then, as-synthesized KAPs with large surface areas, unique pore structures and high thermal stability were prepared as solid-phase microextraction (SPME) coatings that exhibited good extraction abilities for a series of benzene compounds (i.e., benzene, toluene, ethylbenzene and m-xylene, which are referred to as BTEX) and polycyclic aromatic hydrocarbons (PAHs). Under the optimized conditions, the methodologies established for the determination of BTEX and PAHs using the KAPs-triPB and KAPs-B coatings, respectively, possessed wide linear ranges, low limits of detection (LODs, 0.10-1.13ngL(-1) for BTEX and 0.05-0.49ngL(-1) for PAHs) and good reproducibility. Finally, the proposed methods were successfully applied to the determination of BTEX and PAHs in environmental water samples, and satisfactory recoveries (93.6-124.2% for BTEX and 77.2-113.3% for PAHs) were achieved. This study provides a benchmark for exploiting novel microporous organic polymers (MOPs) for SPME applications. PMID:27155913

  10. Lithium battery with solid polymer electrolyte based on comb-like copolymers

    NASA Astrophysics Data System (ADS)

    Daigle, Jean-Christophe; Vijh, Ashok; Hovington, Pierre; Gagnon, Catherine; Hamel-Pâquet, Julie; Verreault, Serge; Turcotte, Nancy; Clément, Daniel; Guerfi, Abdelbast; Zaghib, Karim

    2015-04-01

    In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10-5 Scm-1) at room temperature owing to the negligible values (<10 kJ mol-1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g-1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly "solvates" Li+ thus slowing Li-ion mobility, and PEGMA chains "solvate" Li ions too strongly, trapping and inhibiting their mobility.

  11. Nanocasting Design and Spatially Selective Sulfonation of Polystyrene-Based Polymer Networks as Solid Acid Catalysts.

    PubMed

    Richter, Felix H; Sahraoui, Laila; Schüth, Ferdi

    2016-09-12

    Nanocasting is a general and widely applied method in the generation of porous materials during which a sacrificial solid template is used as a mold on the nanoscale. Ideally, the resulting structure is the inverse of the template. However, replication is not always as direct as anticipated, so the influences of the degree of pore filling and of potential restructuring processes after removal of the template need to be considered. These apparent limitations give rise to opportunities in the synthesis of poly(styrene-co-divinylbenzene) (PSD) polymer networks of widely varying porosities (BET surface area=63-562 m(2)  g(-1) ; Vtot =0.18-1.05 cm(3)  g(-1) ) by applying a single synthesis methodology. In addition, spatially selective sulfonation on the nanoscale seems possible. Together, nanocasting and sulfonation enable rational catalyst design. The highly porous nanocast and predominantly surface-sulfonated PSD networks approach the activity of the corresponding molecular catalyst, para-toluenesulfonic acid, and exceed those of commercial ion-exchange polymers in the depolymerization of macromolecular inulin. PMID:27561365

  12. Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

    SciTech Connect

    Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

    2013-11-27

    Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10{sup −6} S cm{sup −1} when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H) at 3600–3100 cm{sup −1}, carbonyl (-C=O) at 1750–1650 cm{sup −1} and ether (-C-O-C-) at 1150–1000 cm{sup −1} of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF{sub 3}SO{sub 3} salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF{sub 3}SO{sub 3}.

  13. SOLID RADIOACTIVE WASTE STORAGE TECHNOLOGIES: PERFORMANCE OF A POLYMER SEALANT COATING IN AN ARCTIC MARINE ENVIRONMENT

    SciTech Connect

    COWGILL,M.G.; MOSKOWITZ,P.D.; CHERNAENKO,L.M.; NAZARIAN,A.; GRIFFITH,A.; DIASHEV,A.; ENGOY,T.

    2000-06-14

    This first project, under the auspices of the Arctic Military Environmental Cooperation (AMEC) forum, Project 1.4-1 Solid Radioactive Waste Storage Technologies, successfully demonstrated the feasibility of using a polymer-based coating to seal concrete and steel surfaces from permanent radioactive contamination in an Arctic marine environment. A mobile, self-sufficient spraying device, was developed to specifications provided by the Russian Ministry of Defence Northern Navy and was deployed at the RTP Atomflot site, Murmansk, Russia. Demonstration coatings of Polibrid 705 were applied to concrete surfaces exposed to conditions ranging from indoor pedestrian usage to heavy vehicle passage and container handling in a loading bay. A large steel container was also coated with the polymer, filled with solid radwaste, sealed, and left out of doors and exposed to the full 12 month Arctic weather cycle. The field tests were accompanied by a series of laboratory qualification tests carried out at the research laboratory of ICC Nuclide in St. Petersburg. During the 12-month field tests, the sealant coating showed little sign of degradation except for a few chips and gouge marks on the loading bay surface that were readily repaired. Contamination resulting from radwaste handling was easily removed and the surface was not degraded by contact with the decontamination agents. In the laboratory testing, Polibrid 705 met all the Russian qualification requirements with the exception of flammability. In this last instance, it was decided to restrict application of the coating to land-based facilities. The Russian technical experts from the Ministry of Defence quickly familiarized themselves with the equipment and were able to identify several areas of potential improvement as deployment of the equipment progressed. The prime among these was the desirability of extending the range of the equipment through enlarged gasoline tanks (to permit extended operational times) and longer

  14. Development of a solid polymer electrolyte electrolysis cell module and ancillary components for a breadboard water electrolysis system

    NASA Technical Reports Server (NTRS)

    Porter, F. J., Jr.

    1972-01-01

    Solid polymer electrolyte technology in a water electrolysis system along with ancillary components to generate oxygen and hydrogen for a manned space station application are considered. Standard commercial components are utilized wherever possible. Presented are the results of investigations, surveys, tests, conclusions and recommendations for future development efforts.

  15. Cellulose acetate-lithium bis(trifluoromethanesulfonyl)imide solid polymer electrolyte: ATR-FTIR and ionic conductivity behavior

    NASA Astrophysics Data System (ADS)

    Mohd Razalli, Siti Masyitah; Sheikh Mohd Saaid, Siti Irma Yuana; Marwan Ali, Ab Malik; Hassan, Oskar Hasdinor; Yahya, Muhd Zu Azhan

    2015-05-01

    Solid polymer electrolytes (SPEs) based on cellulose acetate (CA) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are prepared by solution cast technique. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy of the polymer salt complexes are recorded in the frequency range between 400 cm-1 and 4000 cm-1. The shifting of carbonyl band (C=O) at 1737 cm-1 to a lower wavenumber confirms the occurrence of complexation between the polymer and the salt. The electrochemical impedance spectroscopy (EIS) analysis discovered that the film with 25 wt.% of salt shows the highest ionic conductivity at room temperature. The change in real dielectric permittivity (ɛr) as a function of frequency at different salt concentrations which exhibits a dispersive behavior at low frequencies and decays at higher frequencies, shows the electrode polarization and space charge effect. The real modulus formalism (Mr) analysis shows that the polymer electrolytes in this work are ionic conductors.

  16. Structural and transport properties of PVC blend PEG doped with Mg(ClO4)2 solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Ramesh, C. H.; Reddy, M. Jaipal; Kumar, J. Siva; Reddy, K. Narasimha

    2014-04-01

    An attempt was made to investigate the effect of Mg(ClO4)2 concentration in PVC-PEG blend polymer electrolyte system. Solid polymer electrolyte films of PVC-PEG-Mg(ClO4)2 have been prepared by using solution - casting process. Structural and transport properties have been studied by employing experimental tools like XRD, FT-IR and DC electrical conductivity. The XRD, FTIR studies were confirmed the formation of a polymer-salt complex. The conductivity results indicated that the incorporation of Mg(ClO4)2 salt into PVC-PEG polymer; at low concentrations the increase in the conductivity is large, but at higher concentrations the increase in conductivity is modest. Using this electrolyte, an electrochemical cells have been fabricated with the configuration Mg/ (PVC-PEG-Mg(ClO4)2) electrolyte / (I2 + C + electrolyte) and its discharge characteristics were determined.

  17. Conductivity study and fourier transform infrared (FTIR) characterization of methyl cellulose solid polymer electrolyte with sodium iodide conducting ion

    SciTech Connect

    Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom

    2015-08-28

    Sodium ion (Na{sup +}) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na{sup +} conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10{sup −11} S/cm.The conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10{sup −5} S/cm.

  18. Equilibrium flattening process of irreversibly adsorbed polymer chains on a solid

    NASA Astrophysics Data System (ADS)

    Sen, Mani; Jiang, Naisheng; Endoh, Maya; Koga, Tadanori; Kawaguchi, Daisuke; Tanaka, Keiji

    We here report the equilibrium process of adsorbed polymer chains on a solid by sum frequency generation (SFG) spectroscopy. Polystyrene (PS,Mw = 290 kDa) thin films prepared onto quartz prisms (a weakly attractive system) were used as a model system. Spin-cast PS 50 nm films on quartz surface (QS) were annealed at 150 °C >Tg for up to 100 h and subsequently rinsed with chloroform to derive the ``flattened chains'' that lie flat onto the substrate surface. The SFG results for the ``matured'' flattened chains after annealing for 96 h revealed the strong interfacial orientation of the backbone chains and weak orientation of PS phenyl rings at the QS which is in contrast to a PS spin-cast film annealed at 150 °C for 1 h: the phenyl rings were strongly directed toward the QS, while the backbone chains were weakly orientated at the QS. We postulate that the increase in the number of solid/segment contacts of the backbone chains is the driving force for this equilibrium flattening process. We will also discuss the generality of this flattening process by using solvent-cast PS thin films where the chains are randomly oriented near the QS. Acknowledgement: NSF Grant No. CMMI-1332499.

  19. Performance of reinforced polymer ablators exposed to a solid rocket motor exhaust. Technical report

    SciTech Connect

    Boyer, C.; Burgess, T.; Bowen, J.; Deloach, K.; Talmy, I.

    1992-10-01

    Summarized in this report is the effort by the Naval Surface Warfare Center Dahlgren Division (NSWCDD) and FMC Corporation (a launcher manufacturer) to identify new high performance ablators suitable for use on Navy guided missile launchers (GML) and ships' structures. The goal is to reduce ablator erosion by 25 to 50 percent compared to that of the existing ablators such as MXBE350 (rubbermodified phenolic containing glass fiber reinforcement). This reduction in erosion would significantly increase the number of new missiles with higher-thrust, longer burn rocket motors that can be launched prior to ablator refurbishment. In fact, there are a number of new Navy missiles being considered for development and introduction into existing GML: e.g., the Antisatellite Missile (ASM) and the Theater High-Altitude Area Defense (THAAD) Missile. The U.S. Navy experimentally evaluated the eight best fiber-reinforced, polymer composites from a possible field of 25 off-the-shelf ablators previously screened by FMC Corporation. They were tested by the Navy in highly aluminized solid rocket motor exhaust plumes to determine their ability to resist erosion and to insulate.... Ablator, Guided Missile Launchers, Erosion, Tactical missiles, Convective heating, Solid rocket motors, Aluminum oxide particles.

  20. Controlled ink-jet printing and deposition of organic polymers and solid particles

    NASA Astrophysics Data System (ADS)

    Perçin, Gökhan; Lundgren, Thomas S.; Khuri-Yakub, Butrus T.

    1998-10-01

    In this letter, we present a technique for the deposition of inks, organic polymers and solid particles, using a fluid ejector. The ejector design is based on a flextensional transducer that excites axisymmetric resonant modes in a clamped circular membrane. It is constructed by bonding a thin piezoelectric annular ring to a thin, edge supported, circular membrane. Liquids or solid particles are placed behind one face of the membrane which has a small orifice (50-200 μm diam) at its center. By applying an ac signal across the piezoelectric element, continuous or drop-on-demand ejection of photoresist (Shipley Microposit S1400-21, S1400-27, S1805, and S1813), oil-based ink, water, or talcum powder [Mg3Si4O10(OH)2] has been achieved. Successful deposition of photoresist has been accomplished without spinning, and thus without waste. Patterning of 10 μm features, by baking, exposure, and developing, has revealed no defects in the deposition process. A boundary integral method was used to numerically simulate drop formation from the vibrating orifice. Simulations have been used to optimize ejection performance.

  1. The influence of the solid/liquid interface on the dewetting of ultra thin polymer films

    NASA Astrophysics Data System (ADS)

    Lessel, Matthias; Klos, Mischa; Baeumchen, Oliver; Jacobs, Karin

    2012-02-01

    In recent years, many studies showed that a thin liquid film on a solid surface in air bears more complexity than expected from a simple three-layer-system: e.g. a highly mobile surface layer in case the liquid is an unentangled polystyrene (PS) melt (Yang et al., Science 2010; Seemann et al., J. of Polym. Sci. 2006) or the PS melt can slip over the solid substrate (Baeumchen et al., PRL 2009). Our study focuses on such phenomena and explores their influence on dewetting (speed, morphology, etc.). We use hydrophilic and -phobic Si wafer (either covered by a highly ordered silane layer or by a thin layer of an amorphous fluoropolymer, AF 1600). On each of the substrates, one expects for a certain set of parameters spinodal dewetting for the PS melt. Yet experimentally, a much higher hole density is observed for both types of hydrophobic wafers than is theoretically expected. Moreover, the two hydrophobic coatings induce different dewetting speeds: the PS melt dewets faster on the silane covered Si wafer. The difference is attributed to slip (silane) or to no slip (AF 1600) conditions at the PS/substrate interface, which is also observable in the type of liquid front profile, which in turn changes the dewetting morphology.

  2. Molecular dynamics of neutral polymer bonding agent (NPBA) as revealed by solid-state NMR spectroscopy.

    PubMed

    Hu, Wei; Su, Yongchao; Zhou, Lei; Pang, Aimin; Cai, Rulin; Ma, Xingang; Li, Shenhui

    2013-01-01

    Neutral polymer bonding agent (NPBA) is one of the most promising polymeric materials, widely used in nitrate ester plasticized polyether (NEPE) propellant as bonding agent. The structure and dynamics of NPBA under different conditions of temperatures and sample processing are comprehensively investigated by solid state NMR (SSNMR). The results indicate that both the main chain and side chain of NPBA are quite rigid below its glass transition temperature (Tg). In contrast, above the Tg, the main chain remains relatively immobilized, while the side chains become highly flexible, which presumably weakens the interaction between bonding agent and the binder or oxidant fillers and in turn destabilizes the high modulus layer formed around the oxidant fillers. In addition, no obvious variation is found for the microstructure of NPBA upon aging treatment or soaking with acetone. These experimental results provide useful insights for understanding the structural properties of NPBA and its interaction with other constituents of solid composite propellants under different processing and working conditions. PMID:24451254

  3. Structure and Ion Transport Studies of PEO-Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Karlinsey, Robert L.; Aravinda Narayanan, R.; Bronstein, Lyudmila M.; Zwanziger, Josef W.

    2003-03-01

    X-ray and conductivity experiments have been performed to understand cation transport in polyethylene (PEO)-based organic-inorganic nanocomposite (OIC) solid polymer electrolytes [1], (PEO)14LiTf + OIC. X-ray diffraction patterns show that the addition of OIC enhances amorphicity, which is thought to aid ionic conduction [2]. The resulting disorder is reflected in changes in intensity and width of the prominent PEO peaks, d120 and d014, which are correlated with the observed maximum in conductivity near 40Further support for the correlation between structure and dynamics is provided by Raman, IR, and DSC measurements. The results are also likely to bear upon the existing theories to understand ionic conduction in crystalline [3] and amorphous [2] phases of materials. This work was funded by a NASA grant (NAG3-2588). [1] L.M. Bronstein, C. Joo, R.L. Karlinsey, A. Ryder, J.W.Zwanziger, Chem. Mat. 13 (2001) 3678. [2] C. Berthier, W. Gorecki, M. Minier, M.B. Armand, J.M. Chabagno, P. Rigaud, Solid State Ionics 11 (1983) 91. [3] J. Gadjourva, Y.G. Andreev, D.P. Tunstall, P.G. Bruce, Nature 412 (2001) 520.

  4. New in situ crosslinking chemistries for hydrogelation

    NASA Astrophysics Data System (ADS)

    Roberts, Meredith Colleen

    Over the last half century, hydrogels have found immense value as biomaterials in a vast number of biomedical and pharmaceutical applications. One subset of hydrogels receiving increased attention is in situ forming gels. Gelling by either bioresponsive self-assembly or mixing of binary crosslinking systems, these technologies are useful in minimally invasive applications as well as drug delivery systems in which the sol-to-gel transition aids the formulation's performance. Thus far, the field of in situ crosslinking hydrogels has received limited attention in the development of new crosslinking chemistries. Moreover, not only does the chemical nature of the crosslinking moieties allow these systems to perform in situ, but they contribute dramatically to the mechanical properties of the hydrogel networks. For example, reversible crosslinks with finite lifetimes generate dynamic viscoelastic gels with time-dependent properties, whereas irreversible crosslinks form highly elastic networks. The aim of this dissertation is to explore two new covalent chemistries for their ability to crosslink hydrogels in situ under physiological conditions. First, reversible phenylboronate-salicylhydroxamate crosslinking was implemented in a binary, multivalent polymeric system. These gels formed rapidly and generated hydrogel networks with frequency-dependent dynamic rheological properties. Analysis of the composition-structure-property relationships of these hydrogels---specifically considering the effects of pH, degree of polymer functionality, charge of the polymer backbone and polymer concentration on dynamic theological properties---was performed. These gels demonstrate diverse mechanical properties, due to adjustments in the binding equilibrium of the pH-sensitive crosslinks, and thus have the potential to perform in a range of dynamic or bioresponsive applications. Second, irreversible catalyst-free "click" chemistry was employed in the hydrogelation of multivalent azide

  5. Preparation and discharge characteristics of solid redox polymerization electrodes employing disulfide polymers and copolymers

    SciTech Connect

    Lerner, M.M. . Dept. of Chemistry); Visco, S.J.; Doeff, M.M.; Dejonghe, L.C. ); Ue, M. )

    1991-01-01

    Recent work in our laboratory on polymeric organodisulfides has shown these materials to perform well as positive electrodes in solid-state batteries. The polymeric materials have been named solid redox polymerization electrodes (SRPE's) due to the reversible polymerization/depolymerization reaction that occurs on charge/discharge of the electrode. The cell radiation for SRPE-based cells can be described for a simple case as, 2n M + (SRS){sub n} = n M{sub 2}SRS, where M is an alkali metal (Li, Na, K) and R is an organic group. In the broader sense SRPE's can have more than two S groups per monomer R unit, and are reversible to other monovalent and divalent metals. In the fully charged state SRPE's consist of polydisulfide polymers and are depolymerized on discharge by scission of sulfur-sulfur bonds, leading to the formation of dithiolate salts in the fully discharged cell. SRPE's are easy to synthesize, are air stable, and should be very inexpensive in bulk quantities. Depending on the redox potential of the polydisulfide and reaction condition, many disulfides can be copolymerized by oxidizing a mixture of dithiols, x HSRSH + y HSR'SH + (x+y)l{sub 2} = (SRS){sub x}(Sr'S){sub y} + 2(x+y) Hl, allowing modification of the physical and/or redox properties of the SRPE's. A series of simple aliphatic dithiols including (HSCH{sub 2}CH{sub 2}SH), (HSCH{sub 2}CH{sub 2}OCH{sub 2}CH{sub 2}SH), and (HSCH{sub 2}CH{sub 2}SCH{sub 2}CH{sub 2}SH) have been oxidized to polydisulfides and mixtures of the dithiols have been copolymerized. All of the resulting polymers and copolymers were evaluated in solid-state lithium cells, with some of the new materials demonstrating high levels of performance. The utilization of available capacity in the positive electrode was observed to be independent of electrode thickness for a number of SRPE's of loading levels up to 45% by weight. 8 refs., 5 figs. 2 tabs.

  6. Core-shell SiO2 -coated Fe3 O4 with a surface molecularly imprinted polymer coating of folic acid and its applicable magnetic solid-phase extraction prior to determination of folates in tomatoes.

    PubMed

    Areerob, Yonrapach; Sricharoen, Phitchan; Limchoowong, Nunticha; Chanthai, Saksit

    2016-08-01

    A novel core-shell magnetic surface molecularly imprinted polymer with folic acid as a template was successfully synthesized by the sol-gel method. To generate Lewis acid sites in the silica matrix for the interaction of the metal coordinate with the template, 3-aminopropyltriethoxysilane was used as a functional monomer, tetraethyl orthosilicate as a cross-linker, and aluminum ions as a dopant. The magnetite encapsulated by the silica shell plays an important role as a magnetic-coated polymer. The synthesized product was characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and FTIR and UV/Vis spectroscopy. The powder X-ray diffraction patterns, FTIR and UV/Vis spectra confirmed the characteristics of the as-prepared silica coated magnetite and folic acid molecularly imprinted polymer. It was successfully applied for magnetic solid-phase extraction prior to the determination of folates in tomato samples using high-performance liquid chromatography with photodiode array detection. The detection limit of the proposed method was 1.67 μg/L, and results were satisfactory, with a relative standard deviation of < 3.94%. PMID:27296679

  7. Effect of Polymer/Solid and Polymer/Vapor Instantaneous Interfaces on the Interfacial Structure and Dynamics of Polymer Melt Systems.

    PubMed

    Bekele, Selemon; Tsige, Mesfin

    2016-07-19

    Polymers are used in a wide range of applications that involve chemical and physical processes taking place at surfaces or interfaces which influence the interaction between the polymer material and the substance that comes into contact with it. Polymer surfaces are usually modified either chemically or physically for specific applications such as facilitating wetting, reducing friction, and enhancing adhesion. The variety and complexity of surface and interfacial processes requires a molecular-level understanding of the structural and dynamical properties of the surface/interface layer to help in the design of materials with desired functional properties. Using molecular dynamics (MD) simulations, we investigate the structure and dynamics at the surface of polymer films. We find that the density profiles of the films as a function of distance relative to an instantaneous surface have a structure indicative of a layering at the polymer/vapor interface similar to the typical layered structure observed at the polymer/substrate interface. However, the interfacial molecules at the polymer/vapor interface have a higher mobility compared to that in the bulk while the mobility of the molecules is lower at the polymer/substrate interface. Time correlation of the instantaneous polymer/vapor interface shows that surface fluctuations are strongly temperature dependent and are directly related to the mobility of polymer chains near the interface. PMID:27347740

  8. Effect of 457 nm Diode-Pumped Solid State Laser on the Polymerization Composite Resins: Microhardness, Cross-Link Density, and Polymerization Shrinkage

    PubMed Central

    Son, Sung-Ae; Park, Jeong-Kil; Jung, Kyoung-Hwa; Ko, Ching-Chang; Jeong, Chang-Mo

    2015-01-01

    Abstract Objective: The purpose of the present study was to test the usefulness of 457 nm diode-pumped solid state (DPSS) laser as a light source to cure composite resins. Materials and methods: Five different composite resins were light cured using three different light-curing units (LCUs): a DPSS 457 nm laser (LAS), a light-emitting diode (LED), and quartz-tungsten-halogen (QTH) units. The light intensity of LAS was 560 mW/cm2, whereas LED and QTH LCUs was ∼900 mW/cm2. The degree of polymerization was tested by evaluating microhardness, cross-link density, and polymerization shrinkage. Results: Before water immersion, the microhardness of laser-treated specimens ranged from 40.8 to 84.7 HV and from 31.7 to 79.0 HV on the top and bottom surfaces, respectively, and these values were 3.3–23.2% and 2.9–31.1% lower than the highest microhardness obtained using LED or QTH LCUs. Also, laser-treated specimens had lower top and bottom microhardnesses than the other LCUs treated specimens by 2.4–19.4% and 1.4–27.8%, respectively. After ethanol immersion for 24 h, the microhardness of laser-treated specimens ranged from 20.3 to 63.2 HV on top and bottom surfaces, but from 24.9 to 71.5 HV when specimens were cured using the other LCUs. Polymerization shrinkage was 9.8–14.7 μm for laser-treated specimens, and these were significantly similar or lower (10.2–16.0 μm) than those obtained using the other LCUs. Conclusions: The results may suggest that the 457 nm DPSS laser can be used as a light source for light-curing dental resin composites. PMID:25549163

  9. Crosslinking of aromatic polyamides via pendant propargyl groups

    NASA Technical Reports Server (NTRS)

    St.clair, A. K.; St.clair, T. L.; Barrick, J. D.; Campbell, F. J.

    1980-01-01

    Methods for crosslinking N-methyl substituted aromatic polyamides were investigated in an effort to improve the applicability of these polymers as matrix resins for Kavlar trademark fiber composites. High molecular weight polymers were prepared from isophthaloyl dichloride and 4,4'- bis(methylamino)diphenylmethane with varying proportions of the N,N'bispropargyl diamine incorporated as a crosslinking agent. The propargylcontaining diamines were crosslinked thermally and characterized by infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Attempts were also made to crosslink polyamide films by exposure to ultraviolet light, electron beam, and gamma radiation.

  10. Preparation and In Vivo Evaluation of Dichloro(1,2-Diaminocyclohexane)platinum(II)-Loaded Core Cross-Linked Polymer Micelles

    PubMed Central

    Oberoi, Hardeep S.; Nukolova, Natalia V.; Zhao, Yi; Cohen, Samuel M.; Kabanov, Alexander V.; Bronich, Tatiana K.

    2012-01-01

    The therapeutic performance of oxaliplatin can be improved by incorporating the central cis-dichloro(1,2-diaminocyclohexane)platinum(II) (DACHPt) motif into the core cross-linked block copolymer micelles. We describe here the preparation, cellular uptake, and in vivo evaluation of core cross-linked micelles loaded with DACHPt. Stable drug-loaded micelles were prepared at high drug loading (~25 w/w%) and displayed a considerably increased in vitro cytotoxicity compared to free oxaliplatin against A2780 ovarian cancer cells. The DACHPt-loaded micelle formulation was well tolerated in mice and exhibited improved antitumor activity than oxaliplatin alone in an ovarian tumor xenograft model. PMID:22844591

  11. Preparation and characterization of tablet formulation based on solid dispersion of glimepiride and poly(ester amide) hyperbranched polymer.

    PubMed

    Reven, Sebastjan; Homar, Miha; Peternel, Luka; Kristl, Julijana; Žagar, Ema

    2013-01-01

    The feasibility of incorporating a solid dispersion containing poorly soluble antidiabetic drug glimepiride and poly(ester amide) hyperbranched polymer into a tablet using a direct-compression tabletting technique was investigated. Tablet cores were additionally coated with hydroxypropyl methylcellulose phthalate in order to protect the extremely hygroscopic solid dispersion from atmospheric moisture. Preliminary stability studies show that glimepiride, which is in amorphous form within solid dispersion, is chemically stable, even if tablets are exposed to elevated temperature and/or moisture. In-vitro dissolution studies show some impact of storage conditions on the tablet cores disintegration time and, consequently, drug release rate. Glimepiride solubility also deteriorates somewhat, most probably due to its partial recrystallization. Storage conditions much less affect the physical stability of coated tablets, which was ascribed to reduced tablet hygroscopicity due to the presence of protecting coating. The hyperbranched polymers are rather new and complex macromolecules. Therefore, we addressed also the biocompatibility of hyperbranched polymer, i.e., its impact on haemolysis of the red blood cells. The concentration required for the haemolytic effect on the red blood cells is around 100-times higher than its expected gastrointestinal luminal concentration, which makes the occurrence of hyperbranched polymer mediated cytotoxicity very unlikely. PMID:21812524

  12. Development of orodispersible polymer films with focus on the solid state characterization of crystalline loperamide.

    PubMed

    Woertz, Christina; Kleinebudde, Peter

    2015-08-01

    The formulation of active pharmaceutical ingredients (API) as orodispersible films is gaining interest among novel oral drug delivery systems due to their small size, enhanced flexibility and improved patient compliance. The aim of this work was the preparation and characterization of orodispersible films containing loperamide hydrochloride (LPH) as model drug. As loperamide hydrochloride is poorly soluble in water it was used in crystalline form with a loading of 2mg/6cm(2) film. Hydroxypropyl methylcellulose (HPMC) and different types of hydroxypropyl cellulose (HPC) in different concentrations were used as film forming polymers whereas arabic gum, xanthan gum and tragacanth served as thickening agents. Films were characterized with respect to the content uniformity, morphology, thermal behavior and crystallinity. Suspensions were investigated regarding their viscosity using a rotational rheometer and the crystal structure of the Active Pharmaceutical Ingredient (API) was analyzed using polarized light microscopy. The development of flexible, non-brittle and homogeneous films of LPH was feasible. Two polymorphic forms of LPH appeared in the film formulations dependent on the utilized polymer. While in presence of HPMC the original polymorphic form I remained stable in suspension and films, the polymorphic form II occurred in presence of HPC. Both polymorphic forms were prepared separately and a solid state characterization was performed. Polymorph I showed isometric crystals whereas polymorph II showed needle shaped crystals. Tragacanth was able to prevent the transformation to polymorph II, if it was dissolved first before HPC. When HPC was added first to the suspension, the conversion to form II occurred irreversibly also after further addition of tragacanth. PMID:25976316

  13. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    NASA Astrophysics Data System (ADS)

    Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2016-09-01

    Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

  14. Physicochemical properties of tadalafil solid dispersions - Impact of polymer on the apparent solubility and dissolution rate of tadalafil.

    PubMed

    Wlodarski, K; Sawicki, W; Haber, K; Knapik, J; Wojnarowska, Z; Paluch, M; Lepek, P; Hawelek, L; Tajber, L

    2015-08-01

    To improve solubility of tadalafil (Td), a poorly soluble drug substance (3μg/ml) belonging to the II class of the Biopharmaceutical Classification System, its six different solid dispersions (1:1, w/w) in the following polymers: HPMC, MC, PVP, PVP-VA, Kollicoat IR and Soluplus were successfully produced by freeze-drying. Scanning electron microscopy showed a morphological structure of solid dispersions typical of lyophilisates. Apparent solubility and intrinsic dissolution rate studies revealed the greatest, a 16-fold, increase in drug solubility (50μg/ml) and a significant, 20-fold, dissolution rate enhancement for the Td/PVP-VA solid dispersion in comparison with crystalline Td. However, the longest duration of the supersaturation state in water (27μg/ml) over 24h was observed for the Td solid dispersion in HPMC. The improved dissolution of Td from Td/PVP-VA was confirmed in the standard dissolution test of capsules filled with solid dispersions. Powder X-ray diffraction and thermal analysis showed the amorphous nature of these binary systems and indicated the existence of dispersion at the molecular level and its supersaturated character, respectively. Nevertheless, as evidenced by film casting, the greatest ability to dissolve Td in polymer was determined for PVP-VA. The crystallization tendency of Td dispersed in Kollicoat IR could be explained by the low Tg (113°C) of the solid dispersion and the highest difference in Hansen solubility parameters (6.8MPa(0.5)) between Td and the polymer, although this relationship was not satisfied for the partially crystalline dispersion in PVP. Similarly, no correlation was found between the strength of hydrogen bonds investigated using infrared spectroscopy and the physical stability of solid dispersions or the level of supersaturation in aqueous solution. PMID:25998701

  15. Polymic protic salt membranes, a new approach to the Holy Grail of a solid state proton conductor

    NASA Astrophysics Data System (ADS)

    Gervasio, Don

    2007-03-01

    Electrons are readily transported in solids through the electronic conduction band in metals and semiconductors, but ion conduction is not as simple. Most proton conductors are aqueous solutions. Water plays two roles: i) water ionizes dissolved acids (and bases), and ionic conductivity results from the diffusion of protons and anions, a vehicular mechanism; ii) water also has an accessible ``proton hopping path'' (proton transport via hydrogen bonding and rotations) resulting in higher solution conductivity than by diffusion of ions alone. Some liquids, like phosphoric acid, have been know to conduct only protons with no co-transport of other species, but until recently these have been few in number. Some solids, like polyguanine, conduct only protons, but there have been even fewer reports of these. A proton transfer salt is an equimolar mixture of an acid and a base that internally transfer a proton. Recently, a number of proton transfer salts in the liquid state have been found that can transport proton without water, even at temperatures well above the boiling point of water. Whether a vehicular or hopping transport mechanism operates for these liquid proton transfer salts is under study. Vehicular transport is not possible in a solid membrane made for proton transfer salt formed from a solid polymer with one moiety (e.g., base) covalently fixed into the polymer and with the other moiety (e.g., acid) electrostatically bound after proton transfer. Synthetic strategies and characterization of solid proton conducting membranes, including solid protic transfer salt membranes, will be presented.

  16. 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.

  17. Flexible thin-film battery based on graphene-oxide embedded in solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Kammoun, M.; Berg, S.; Ardebili, H.

    2015-10-01

    Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending.Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method

  18. Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Manko, David J.; Enayatullah, Mohammad; Appleby, A. John

    1989-01-01

    High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

  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. Formulation and Characterization of Solid Dispersion Prepared by Hot Melt Mixing: A Fast Screening Approach for Polymer Selection

    PubMed Central

    Enose, Arno A.; Dasan, Priya K.; Sivaramakrishnan, H.; Shah, Sanket M.

    2014-01-01

    Solid dispersion is molecular dispersion of drug in a polymer matrix which leads to improved solubility and hence better bioavailability. Solvent evaporation technique was employed to prepare films of different combinations of polymers, plasticizer, and a modal drug sulindac to narrow down on a few polymer-plasticizer-sulindac combinations. The sulindac-polymer-plasticizer combination that was stable with good film forming properties was processed by hot melt mixing, a technique close to hot melt extrusion, to predict its behavior in a hot melt extrusion process. Hot melt mixing is not a substitute to hot melt extrusion but is an aid in predicting the formation of molecularly dispersed form of a given set of drug-polymer-plasticizer combination in a hot melt extrusion process. The formulations were characterized by advanced techniques like optical microscopy, differential scanning calorimetry, hot stage microscopy, dynamic vapor sorption, and X-ray diffraction. Subsequently, the best drug-polymer-plasticizer combination obtained by hot melt mixing was subjected to hot melt extrusion process to validate the usefulness of hot melt mixing as a predictive tool in hot melt extrusion process. PMID:26556187