Sample records for styrene block polymers

  1. 21 CFR 177.1810 - Styrene block polymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

  2. Poly(styrene-divinylbenzene) beads surface functionalized with di-block polymer grafting and multi-modal ligand attachment: performance of reversibly immobilized lipase in ester synthesis. (United States)

    Bayramoglu, Gulay; Karagoz, Bunyamin; Altintas, Begum; Arica, M Yakup; Bicak, Niyazi


    Fibrous poly(styrene-b-glycidylmethacrylate) brushes were grafted on poly(styrene-divinylbenzene) (P(S-DVB)) beads using surface-initiated atom transfer radical polymerization. Tetraethyldiethylenetriamine (TEDETA) ligand was incorporated on P(GMA) block. The ligand attached beads were used for reversible immobilization of lipase. The influences of pH, ionic strength, and initial lipase concentration on the immobilization capacities of the beads have been investigated. Lipase adsorption capacity of the beads was about 78.1 mg/g beads at pH 6.0. The Km value for immobilized lipase was about 2.1-fold higher than that of free enzyme. The thermal, and storage stability of the immobilized lipase also was increased compared to the native lipase. It was observed that the same support enzyme could be repeatedly used for immobilization of lipase after regeneration without significant loss in adsorption capacity or enzyme activity. A lipase from Mucor miehei immobilized on styrene-divinylbenzene copolymer was used to catalyze the direct esterification of butyl alcohol and butyric acid.

  3. 40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified styrene, divinylbenzene polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical...

  4. Morphology-properties relationship on nanocomposite films based on poly(styrene-block-diene-block-styrene copolymers and silver nanoparticles

    Directory of Open Access Journals (Sweden)


    Full Text Available A comparative study on the self-assembled nanostructured morphology and the rheological and mechanical properties of four different triblock copolymers, based on poly(styrene-block-diene-block-styrene and poly(styrene-block-diene-block-styrene matrices, and of their respective nanocomposites with 1 wt% silver nanoparticles, is reported in this work. In order to obtain well-dispersed nanoparticles in the block copolymer matrix, dodecanethiol was used as surfactant, showing good affinity with both nanoparticles and the polystyrene phase of the matrices as predicted by the solubility parameters calculated based on Hoftyzer and Van Krevelen theory. The block copolymer with the highest PS content shows the highest tensile modulus and tensile strength, but also the smallest elongation at break. When silver nanoparticles treated with surfactant were added to the block copolymer matrices, each system studied shows higher mechanical properties due to the good dispersion and the good interface of Ag nanoparticles in the matrices. Furthermore, it has been shown that semiempirical models such as Guth and Gold equation and Halpin-Tsai model can be used to predict the tensile modulus of the analyzed nanocomposites.

  5. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY... from the requirement of a tolerance for residues of styrene-ethylene-propylene block copolymer (CAS Reg... permissible level for residues of styrene-ethylene-propylene block copolymer on food or feed commodities...

  6. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of styrene, cyclohexyl... Significant New Uses for Specific Chemical Substances § 721.9492 Polymers of styrene, cyclohexyl methacrylate...) The chemical substances identified generically as polymers of styrene, cyclohexyl methacrylate and...

  7. -Styrene)

    KAUST Repository

    Sutisna, Burhannudin


    Membranes are prepared by self-assembly and casting of 5 and 13 wt% poly(styrene-b-butadiene-b-styrene) (PS-b-PB-b-PS) copolymers solutions in different solvents, followed by immersion in water or ethanol. By controlling the solution-casting gap, porous films of 50 and 1 µm thickness are obtained. A gradient of increasing pore size is generated as the distance from the surface increased. An ordered porous surface layer with continuous nanochannels can be observed. Its formation is investigated, by using time-resolved grazing incident small angle X-ray scattering, electron microscopy, and rheology, suggesting a strong effect of the air-solution interface on the morphology formation. The thin PS-b-PB-b-PS ordered films are modified, by promoting the photolytic addition of thioglycolic acid to the polybutadiene groups, adding chemical functionality and specific transport characteristics on the preformed nanochannels, without sacrificing the membrane morphology. Photomodification increases fivefold the water permeance to around 2 L m(-2) h(-1) bar(-1) , compared to that of the unmodified one. A rejection of 74% is measured for methyl orange in water. The membranes fabrication with tailored nanochannels and chemical functionalities can be demonstrated using relatively lower cost block copolymers. Casting on porous polyacrylonitrile supports makes the membranes even more scalable and competitive in large scale.

  8. Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers (United States)

    Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

    Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

  9. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted... (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

  10. 76 FR 77709 - Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption AGENCY...-propenoate and ethenylbenzene (CAS Reg. No. 25036-16-2); also known as butyl acrylate-methacrylic acid...-risk polymers are described in 40 CFR 723.250(d). Butyl acrylate-methacrylic acid-styrene polymer...

  11. Modification of poly(styrene-block-butadiene-block-styrene) [SBS] with phosphorus containing fire retardants

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Ullah, Saif; Jomaas, Grunde


    An elaborate survey of the chemical modification methods for endowing highly flammable SBS with increased fire resistant properties by means of chemical modification of the polymer backbone with phosphorus containing fire retardant species is presented. Optimal conditions for free radical additio...... application of the H3PO4 modified SBS as a fire retardant additive for bitumen material, in combination with synergetic melamine species, offered 25% better self-extinguishing properties of such formulation already at a low loading level of the fire retardant components (3.5 wt.%)....

  12. 40 CFR 721.7020 - Distillates (petroleum), C(3-6), polymers with styrene and mixed terpenes (generic name). (United States)


    ...), polymers with styrene and mixed terpenes (generic name). 721.7020 Section 721.7020 Protection of...), C(3-6), polymers with styrene and mixed terpenes (generic name). (a) Chemical substance and...), polymers with styrene and mixed terpenes (PMN P-89-676) is subject to reporting under this section for the...

  13. Toxicity of the components of styrene polymers: polystyrene, acrylonitrile-butadiene-styrene (ABS) and styrene-butadiene-rubber (SBR). Reactants and additives. (United States)

    Fishbein, L


    The toxicity of the components of styrene polymers, e.g., polystyrene, ABS and SBR, were reviewed with primary focus on the reactive monomers (except styrene) (e.g., acrylonitrile, butadiene) as well as on impurities and solvents such as benzene, hexane and methylethyl ketone, and additives such as phenyl-2-naphthylamine, di-n-butyl phthalate, and a number of peroxide initiators and flame retardants (e.g., 2,3-dibromopropanol, decadibromodiphenyl oxide and antimony trioxide). It is stressed that toxicity data are generally lacking for the majority of additives employed in the production of styrene polymers. Information is also lacking as to the numbers of individuals at potential risk and the extent of their exposure to the large number of additives employed.

  14. Surfactant effects on morphology-properties relationships of silver-poly(styrene-b-isoprene-b-styrene) block copolymer nanocomposites. (United States)

    Peponi, Laura; Tercjak, Agnieszka; Torre, Luigi; Kenny, Josè M; Mondragon, Iñaki


    Good dispersion of silver nanoparticles in poly(styrene-b-isoprene-b-styrene) block copolymer matrix has been achieved by adding dodecanethiol as surfactant to lower the high surface energy of metal nanoparticles. First, the influence of surfactant in the cylindrical nanostructure of neat block copolymer matrix has been analyzed. Taking into account the high solubility between dodecanethiol and the PS block of the SIS block copolymer, when silver nanoparticles and surfactant have been added to the block copolymer matrix its morphology changes from cylindrical to lamellar nanostructure. For the nanocomposite without surfactant, the block copolymer matrix loses its capability to self-assemble in lamellar nanostructure and in this case, agglomeration of silver nanoparticles occurs. Rheological, mechanical and morphological analysis were carried out in order to study the optimal content of surfactant necessary to obtain well-dispersed nanoparticles without worsen the final properties of the nanocomposite. The best silver/dodecanethiol w/w ratio appears to be 1, as confirmed by UV-Vis analysis. Moreover, semi-empirical models, such as Guth and Gold, and Halpin-Tsai, have been used in order to both predict and verify experimental tensile modulus of the obtained nanocomposites. The Guth and Gold equation, applicable to elastomers filled with spherical nanoparticles, provides a result closer to the experimental values than Halpin-Tsai model.

  15. Polymers and block copolymers of fluorostyrenes by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian


    Fully or partly fluorinated polymers have many desirable and intriguing properties. In the framework of a larger program on design and control of new functional block copolymers we recently employed the Atom Transfer Radical Polymerization (ATRP) protocol on 2,3,4,5,6-pentafluorostyrene (FS). We...... materials based on 2,3,5,6-tetrafiuoro-4-methoxy-styrene (TFMS). TFMS homopolymers as well as diblock copolymers with FS are produced by ATRP. Both types of novel polymers were subsequently demethylated and different side chains introduced on the resulting hydroxy sites....

  16. Volume shrinkage and rheological studies of epoxidised and unepoxidised poly(styrene-block-butadiene-block-styrene) triblock copolymer modified epoxy resin-diamino diphenyl methane nanostructured blend systems. (United States)

    George, Sajeev Martin; Puglia, Debora; Kenny, Josè M; Parameswaranpillai, Jyotishkumar; Vijayan P, Poornima; Pionteck, Jűrgen; Thomas, Sabu


    Styrene-block-butadiene-block-styrene (SBS) copolymers epoxidised at different epoxidation degrees were used as modifiers for diglycidyl ether of the bisphenol A-diamino diphenyl methane (DGEBA-DDM) system. Epoxy systems containing modified epoxidised styrene-block-butadiene-block-styrene (eSBS) triblock copolymer with compositions ranging from 0 to 30 wt% were prepared and the curing reaction was monitored in situ using rheometry and pressure-volume-temperature (PVT) analysis. By controlling the mole percent of epoxidation, we could generate vesicles, worm-like micelles and core-shell nanodomains. At the highest mole percent of epoxidation, the fraction of the epoxy miscible component in the triblock copolymer (epoxidised polybutadiene (PB)) was maximum. This gave rise to core-shell nanodomains having a size of 10-15 nm, in which the incompatible polystyrene (PS) becomes the core, the unepoxidised PB becomes the shell and the epoxidised PB interpenetrates with the epoxy phase. On the other hand, the low level of epoxidation gave rise to bigger domains having a size of ∼1 μm and the intermediate epoxidation level resulted in a worm-like structure. This investigation specifically focused on the importance of cure rheology on nanostructure formation, using rheometry. The reaction induced phase separation of the PS phase in the epoxy matrix was carefully explored through rheological measurements. PVT measurements during curing were carried out to understand the volume shrinkage of the blend, confirming that shrinkage behaviour is related to the block copolymer phase separation process during curing. The volume shrinkage was found to be maximum in the case of blends with unmodified SBS, where a heterogeneous morphology was observed, while a decrease in the shrinkage was evidenced in the case of SBS epoxidation. It could be explained by two effects: (1) solubility of the epoxidised block copolymer in the DGEBA leads to the formation of nanoscopic domains upon

  17. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves. (United States)

    Brubert, Jacob; Krajewski, Stefanie; Wendel, Hans Peter; Nair, Sukumaran; Stasiak, Joanna; Moggridge, Geoff D


    Certain styrenic thermoplastic block copolymer elastomers can be processed to exhibit anisotropic mechanical properties which may be desirable for imitating biological tissues. The ex-vivo hemocompatibility of four triblock (hard-soft-hard) copolymers with polystyrene hard blocks and polyethylene, polypropylene, polyisoprene, polybutadiene or polyisobutylene soft blocks are tested using the modified Chandler loop method using fresh human blood and direct contact cell proliferation of fibroblasts upon the materials. The hemocompatibility and durability performance of a heparin coating is also evaluated. Measures of platelet and coagulation cascade activation indicate that the test materials are superior to polyester but inferior to expanded polytetrafluoroethylene and bovine pericardium reference materials. Against inflammatory measures the test materials are superior to polyester and bovine pericardium. The addition of a heparin coating results in reduced protein adsorption and ex-vivo hemocompatibility performance superior to all reference materials, in all measures. The tested styrenic thermoplastic block copolymers demonstrate adequate performance for blood contacting applications.

  18. The effect of multifunctional monomers/oligomers Additives on electron beam radiation crosslinking of poly (styrene-block-isoprene/butadiene-block-styrene) (SIBS) (United States)

    Wu, Jinping; Soucek, Mark D.


    The effect of multifunctional monomers or oligomers (MFM/O) additives on electron beam (E-beam) radiation induced crosslinking of poly (styrene-block-isoprene/butadiene-block-styrene) (SIBS) was studied. Ten types of MFM/O were investigated, including trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triallyl cyanurate (TAC), polybutadiene diacrylate (PB-diacrylate), ethylene glycol dimethylacrylate (EGDMA), butylene glycol dimethacrylate (BGDMA), 1,2-polybutadiene. The effects of MFM/O concentration and E-beam radiation dose on properties of SIBS were studied including tensile strength, elongation-at-break, modulus, gel content, equilibrium swelling and crosslink density. TMPTA significantly improved the tensile modulus and crosslink density of SIBS. SIBS with TMPTMA and TMTPMA with inhibitor showed a 50% increase in tensile strength. The solubility of MFM/O in SIBS was also investigated by a selective swelling method. The MFM/O were found to be soluble in both phases of SIBS. The viscosity of SIBS with methacrylate type MFM/O was stable at 200 °C.

  19. Sulfonation and characterization of styrene-indene copolymers for the development of proton conducting polymer membranes

    Directory of Open Access Journals (Sweden)

    Cristiane M. Becker


    Full Text Available The aim of this work is to obtain polymer precursors based on styrene copolymers with distinct degrees of sulfonation, as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the performance of the polyelectrolyte was evaluated based on the content of acid polar groups incorporated into the macromolecular chain. Polymeric films were produced by blending the sulfonated styrene-indene copolymer with poly(vinylidene fluoride. The degree of sulfonation of the polymer was strongly affected by the sulfonation reaction parameters, with a direct impact on the ionic exchange capacity and the ionic conductivity of the sulfonated polymers and the membranes obtained from them. The films produced with the blends showed more suitable mechanical properties, although the conductivity of the membranes was still lower than that of commercially available membranes used in fuel cells.

  20. Complexation of AB+, AB+C, ACB+, and A(B+-stat-C) block copolymer micelles with poly(styrene sulfonate) as models for tunable gene delivery vectors (United States)

    Laaser, Jennifer; Jiang, Yaming; Lohmann, Elise; Reineke, Theresa; Lodge, Timothy

    We investigate the complexation of poly(styrene sulfonate) with micelles with mixed cationic/hydrophilic coronas as models for tunable gene delivery vectors. The micelles are self-assembled from AB+, AB+C, ACB+, and A(B+-stat-C) block polymer architectures, where the hydrophobic A blocks (poly(styrene)) form the micelle cores, and the cationic B blocks (poly(dimethylamino ethyl methacrylate)) and hydrophilic, nonionic C blocks (poly(poly(ethylene glycol) methyl ether methacrylate)) form the coronas. We find that hydrophilic units do not change the colloidal stability of the complexes, and complexes based on all four micelle architectures form broad, multimodal size distributions. While complexes based on the AB+, AB+C, and ACB+polymer architectures are kinetically trapped at low ionic strength, however, those based on the A(B+-stat-C) architecture rapidly rearrange into single-micelle complexes when the linear polyanion is in excess. This suggests that the randomly-placed hydrophilic units break up the ion pairing between the cationic and anionic chains and promote formation of over-charged complexes. Design of the micelle architecture may thus provide a powerful way control the structure and stability of micelle-polyelectrolyte complexes for gene delivery applications.



    Abdelzaher E. A. Mostafa; Nasser, A M


    According to the most recent surveys, the European area produced 265 mil tons of asphalt for road applications in 2014, while the amount of available Reclaimed Asphalt Pavement (RAP) was more than 50 mil tons. The use of RAP in new blended mixes reduces the need of neat bitumen, making RAP recycling economically attractive. This study investigates the potential use of styrene-bacrylate polymer and extracted Reclaimed Asphalt Pavement (RAP) in Hot Mix Asphalt (HMA) with different percentages b...

  2. Feasibility of Using Foamed Styrene Maleic Anhydride (SMA) Co-polymer in Wood Based Composites


    Mustafa Zor; Nurgul Tankut; Alper Kiziltas; Douglas Gardner; Hikmet Yazici


    Wood plastic composites (WPCs) have often been used in consumer applications, automotive industry and exterior construction. WPCs consist mostly of wood and thermoplastic polymer. WPCs can have superior outdoor durability and much lower maintenance costs than regular wood. WPCs can be used instead of wood. Styrene maleic anhydride (SMA) is used in plastic composites for the automotive industry and also in engineering applications. SMA wood composites, as one of the WPCs using wood fibers as r...

  3. Effect of concentration and humidity on the formation of porous polymer films using Styrene Butadiene Co-Polymer (United States)

    Jose, Renu; Sujith, A.; Predeep, P.


    Honeycomb structured porous materials from complex polymers are formed using water droplet templating method. In the present work microporous films were prepared from styrene butadiene rubber (SBR) using emulsion technique. The pore sizes can be easily tuned by changing the concentration and the humidity condition. The pore size is characterized by optical microscope and Scanning electron microscope (SEM). These films can be used for various applications in optoelectronics, photonics, catalysis, tissue engineering, bioanalytical purposes etc.

  4. Investigation on physical behavior of styrene wood-polymer in different concentrations of monomer

    Directory of Open Access Journals (Sweden)

    maryam ghorbani


    Full Text Available This research was conducted to study the effect of different concentrations of styrene lumen monomer on the physical properties of beech wood. Physical test samples were prepared according to ASTM-D1037 standard and treated with vacuum-pressure method at five concentration levels; 0, 40, 60, 80 and 100 percent of soluble monomer. For polymerization, treated samples were heated in oven for two 24-hour period at 90 and 103ºC respectively. Monomer and polymer absorption, density variation, water absorption, swelling and anti-swelling efficiency (ASE were determined. According to the results, Monomer and polymer absorption were increment by monomer concentration increase, and they were reported 38.2% and 26% in highest level. With polymer absorption enhancement, density of wood increased from 0/63g/cm³ in control to 0/91g/cm³ in the highest monomer concentration level that reduces pores in wood-polymer structure. Absorbed polymer enhancement decreased hydrophilicity and dimensional changes of treated samples, so that water absorption and swelling volume of the samples saturated with 100% concentration of monomer were decreased 64% and 45.3% after the longest immersion time. Highest Anti-swelling efficiency of Styrene-saturated samples was determined 56.15% in the maximum concentration level of treatment.

  5. Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities (United States)

    McLeod, David Charles

    Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

  6. The migration of acrylonitrile from acrylonitrile/butadiene/styrene polymers into food-simulating liquids. (United States)

    Lickly, T D; Markham, D A; Rainey, M L


    The correlation of residual acrylonitrile (AN) monomer concentration in AN-containing polymers with AN migration into food simulants is of interest because the US FDA regulates the use of these polymers on the basis of the amount of AN that may migrate into food simulants. Studies of the migration of AN into water from seven acrylonitrile/butadiene/styrene polymers with varying composition and residual AN levels showed that a linear relationship exists between the concentration of AN in the polymer and the amount of AN migrating, for a given set of exposure conditions. A linear relationship was also observed between the diffusion coefficients generated from the experimental data using a simple Fickian diffusion model and the inverse of the absolute temperature of exposure.

  7. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    applications as, e.g., membranes for separation and purification, templates for nanostructured materials, sensors, substrates for catalysis, low dielectric constant materials, photonic materials, and depots for controlled drug delivery. The development of nanoporous polymers with well controlled pore wall......Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed...

  8. Tracking Solvent Uptake in Block Polymer Thin Films during Solvent Vapor Annealing (United States)

    Shelton, Cameron; Jones, Ronald; Dura, Joseph; Epps, Thomas


    A key goal in the block polymer (BP) thin films community is the design of a template-free, universal annealing method to control nanoscale self-assembly over large length scales. Solvent vapor annealing (SVA) offers a unique solution to this challenge with its ability to tune substrate surface, free surface, and polymer-polymer interactions by exposing films to appropriate solvents. However, there is little understanding of how the solvent behaves during the SVA process. In this work, we utilized the combination of deuterated solvents with small-angle neutron scattering (SANS) and neutron reflectometry to track solvent uptake in poly(styrene-b-isoprene-b-styrene) thin films. Two solvents were chosen for this analysis: d-hexane (isoprene selective) and d-benzene (styrene selective). Our work has shown that solvent choice and partial pressure have a significant impact on how solvent segregates within individual polymer domains and the film as a whole, directly impacting the restructuring of polymer domains. This work provides further understanding of the mechanism behind SVA, thereby making it easier to select appropriate conditions for desired self-assembly control.

  9. Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study (United States)

    Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

    Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

  10. Porous polymers based on aryleneethynylene building blocks. (United States)

    Bunz, Uwe H F; Seehafer, Kai; Geyer, Florian L; Bender, Markus; Braun, Ingo; Smarsly, Emanuel; Freudenberg, Jan


    Porous conjugated polymers are synthesized by metal-catalyzed coupling reactions. The progress for porous polymers when planar or tetrahedral building blocks are connected by alkyne units into novel materials is highlighted. The most prominent reaction for the buildup of the microporous alkyne-bridged polymers is the Sonogashira reaction, connecting alkynes to aromatic iodides or bromides. The availability of the building blocks and the potency of the Sonogashira reaction allow preparing a large variety of intrinsically porous polymeric materials, in which rigid struts connect multipronged centers. The microporous polymers are used as catalysts and as storage materials for gases and sensors. Postfunctionalization schemes, understanding of structure-property relationships, and the quest for high porosity are pertinent. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Microbial production of the aromatic building-blocks (S)-styrene oxide and (R)-1,2-phenylethanediol from renewable resources. (United States)

    McKenna, Rebekah; Pugh, Shawn; Thompson, Brian; Nielsen, David R


    (S)-Styrene oxide and (R)-1,2-phenylethanediol are chiral aromatic molecular building blocks used commonly as precursors to pharmaceuticals and other specialty chemicals. Two pathways have been engineered in Escherichia coli for their individual biosynthesis directly from glucose. The novel pathways each constitute extensions of the previously engineered styrene pathway, developed by co-expressing either styrene monooxygenase (SMO) or styrene dioxygenase (SDO) to convert styrene to (S)-styrene oxide and (R)-1,2-phenylethanediol, respectively. StyAB from Pseudomonas putida S12 was determined to be the most effective SMO. SDO activity was achieved using NahAaAbAcAd of Pseudomonas sp. NCIB 9816-4, a naphthalene dioxygenase with known broad substrate specificity. Production of phenylalanine, the precursor to both pathways, was systematically enhanced through a number of mutations, most notably via deletion of tyrA and over-expression of tktA. As a result, (R)-1,2-phenylethanediol reached titers as high as 1.23 g/L, and at 1.32 g/L (S)-styrene oxide titers already approach their toxicity limit. As with other aromatics, product toxicity was strongly correlated with a model of membrane accumulation and disruption. This study additionally demonstrates that greater flux through the styrene pathway can be achieved if its toxicity is addressed, as achieved in this case by reacting styrene to less toxic products. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Direct Synthesis of Polymer Nanotubes via Aqueous Dispersion Polymerization of Cyclodextrin/Styrene Complex. (United States)

    Chen, Xi; Liu, Lei; Huo, Meng; Zeng, Min; Peng, Liao; Feng, Anchao; Wang, Xiaosong; Yuan, Jinying


    We report a one-step synthesis of nanotubes by RAFT dispersion polymerization of cyclodextrin/styrene (CD/St) complexes directly in water. The resulted amphiphilic PEG-b-PS diblock copolymers self-assemble in situ into nanoparticles with various morphologies. Spheres, worms, lamellae, and nanotubes were controllably obtained. Because of the complexation, the swelling degree of polystyrene (PS) blocks by free St is limited, resulting limited mobility of PS chains. Consequently, kinetically trapped lamellae and nanotubes were obtained instead of spherical vesicles. During the formation of nanotubes, small vesicles firstly formed at the ends of the tape-like lamellae, then grew and fused into nanotubes with limited chain rearrangement. The introduction of host-guest interaction based on CDs enables the aqueous dispersion polymerization of water-immiscible monomers, and produces kinetically trapped nanostructures, which could be a powerful technique for nanomaterials synthesis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Controlling self-assembly and ordering of block polymer nanostructures in thin films (United States)

    Luo, Ming

    Block polymers have garnered significant attention in the past few decades due to their ability to self-assemble into a boundless array of structures such as spheres, cylinders, gyroid, and lamellae. The sizes of the periodical structures typically are 5 - 100 nm, making them ideal for emerging nanotechnologies, such as nanolithography, nanotemplating, nanoporous membranes, and photonics devices. Many of these applications require thin film geometries, in which the block polymers form well-ordered nanostructures and precisely controlled domain orientations. Understanding the factors that affect thin film phase behavior and being able to control the nanostructures, domain orientation, and domain ordering in thin film is essential to realizing the full potential of these unique materials. In this dissertation, I describe significant efforts to manipulate the block polymer thin film structures, direct the nanostructure ordering, and understand the connection between the macromolecular molecular structures and the block polymer properties. First, substrate surface modification with chlorosilane was employed to manipulate the nanostructure of poly(styrene- b-isoprene-b-styrene) (SIS) thin films. A morphological transformation from parallel cylinders to hexagonally perforated lamellae (HPL) was identified, in a high-throughput fashion, using gradient methods. The gradient methods are highly adaptable for the possible universal manipulation of thin film nanostructures. Second, rastering solvent vapor annealing - soft shear method was developed and demonstrated as a simple, yet highly effective method to achieve macroscopic alignment of SIS cylinders. This method substantially improves on previous approaches by using simple instrumentation to unlock an array of alignment patterns with a variety of self-assembling polymers and provides feasibility and flexibility for practical industrial production. Next, the interfacial mixing characteristics of tapered block polymer were

  14. “Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

    Energy Technology Data Exchange (ETDEWEB)

    Vanderlaan, Marie E.; Hillmyer, Marc A. (UMM)


    We report the facile synthesis of well-defined ABA poly(lactide)-block-poly(styrene)-block-poly(lactide) (LSL) triblock copolymers having a disperse poly(styrene) midblock (Ð = 1.27–2.24). The direct synthesis of telechelic α,ω-hydroxypoly(styrene) (HO-PS-OH) midblocks was achieved using a commercially available difunctional free radical diazo initiator 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Poly(lactide) (PLA) end blocks were subsequently grown from HO-PS-OH macroinitiators via ring-opening transesterification polymerization of (±)-lactide using the most common and prevalent catalyst system available, tin(II) 2-ethylhexanoate. Fourteen LSL triblock copolymers with total molar masses Mn,total = 24–181 kg/mol and PLA volume fractions fPLA = 0.15–0.68 were synthesized and thoroughly characterized. The self-assembly of symmetric triblocks was analyzed in the bulk using small-angle X-ray scattering and in thin films using grazing incidence small-angle X-ray scattering and atomic force microscopy. We demonstrate both the bulk and thin film self-assembly of LSL disperse triblocks gave well-organized nanostructures with uniform domain sizes suitable for nanopatterning applications.

  15. Radiation-induced crosslinking of poly(styrene–butadiene–styrene) block copolymers and their sulfonation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sun-Young [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Song, Ju-Myung; Sohn, Joon-Yong [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Shul, Yong-Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Shin, Junhwa, E-mail: [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)


    Highlights: • The c-SBS films were prepared using a gamma ray or electron beam. • The crosslinking degree of the c-SBS films were increased with the irradiation dose. • The prepared c-SBS films were sulfonated with various concentration of CSA. • The sulfonation of the c-SBS film is largely dependent on the concentration of CSA. • The sulfonation process is progressed from the surface to the inner part of c-SBS film. -- Abstract: Several crosslinked poly(styrene–butadiene–styrene) (c-SBS) block copolymer films were prepared using a gamma ray or electron beam with various irradiation doses and the prepared c-SBS film was then subjected to sulfonation using a chlorosulfonic acid (CSA) solution to introduce a sulfonic acid group. To estimate the degree of crosslinking, the gel fractions and FT-IR spectra of the c-SBS films were used and the results indicate that the degree of crosslinking is increased with an increase in the radiation dose. The surface morphology and mechanical property of the c-SBS films were observed using SEM and UTM instruments, respectively. The sulfonated c-SBS films were investigated by measuring the ion exchange capacity (IEC) and by observing the cross-sectional distribution patterns of sulfonic acid group using an SEM-EDX instrument. The IEC and SEM-EDX studies indicate that the sulfonated c-SBS membranes can be successfully prepared through the radiation crosslinking of the SBS film and the subsequent sulfonation with a diluted CSA solution.

  16. Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights

    Directory of Open Access Journals (Sweden)

    Steffen Eggers


    Full Text Available The combination of reversible addition–fragmentation chain transfer (RAFT and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX, increasing the phase transition temperature (PTT of the used thermoresponsive poly(N-acryloylpyrrolidine (PAPy macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine (PDMA-b-P(APi-co-APy as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS block. In dynamic light scattering (DLS, as well as cryo-transmission electron microscopy (cryoTEM, moreover, all created latexes indeed reveal a high (temperature stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

  17. Chitosan/polyanion surface modification of styrene–butadiene–styrene block copolymer membrane for wound dressing

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jen Ming, E-mail: [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Yang, Jhe-Hao [Department of Electronic Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Huang, Huei Tsz [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China)


    The surface of styrene–butadiene–styrene block copolymer (SBS) membrane is modified with tri-steps in this study. At first, two step modified SBS membrane (MSBS) was prepared with epoxidation and ring opening reaction with maleated ionomer. Then chitosan was used as the polycation electrolyte and sodium alginate, poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes to deposit on the surfaces of MSBS membrane by the layer-by-layer self-assembly (LbL) deposition technique to get three [chitosan/polyanion] LbL modified SBS membranes, ([CS/Alg], [CS/PGA] and [CS/PAsp]). From the quantitative XPS analysis and water contact angle measurement, it is found that the order of wettability and the content of functional group percentages of COO{sup −} and -O=C-N- on the three [CS/polyanion] systems are [CS/Alg] > [CS/PGA] > [CS/PAsp]. Performances of water vapor transmission rates, fibronectin adsorption, antibacterial assessment and 3T3 fibroblast cell growth on [CS/Alg], [CS/PGA] and [CS/PAsp] membranes were also evaluated. With the evaluation of water vapor transmission rate, these [CS/Alg], [CS/PGA] and [CS/PAsp] membranes are sterile semipermeable with water evaporation at about 82 ± 8 g/day · m{sup 2}. It is found that the amount of fibronectin adsorption on the three [CS/polyanion] systems is significantly determined by the sum of the functional group of COO{sup −} and -O=C-N- on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp] systems. The results are inverse with the sum of the functional group of COO{sup −} and -O=C-N- on the three [CS/polyanion]. From the cytotoxicity test and cell adhesion and proliferation assay of 3T3 fibroblasts on the three [CS/polyanion] systems, it revealed that the cells not only remained viable but they also proliferated on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp]. The bactericidal activity was found on [CS/Alg], [CS/PGA] and [CS/PAsp]. The transport of bacterial through

  18. Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System

    Directory of Open Access Journals (Sweden)

    Akira Hirao


    Full Text Available This article reviews the successful development of two specially designed linking methodologies in conjunction with a living anionic polymerization system for the synthesis of novel multiblock polymers, composed of three or more blocks, difficult to be synthesized by sequential polymerization. The first methodology with the use of a new heterofunctional linking agent, 2-(4-chloromethylphenylethyldimethylchlorosilane (1, was developed for the synthesis of multiblock polymers containing poly(dimethylsiloxane (PDMS blocks. This methodology is based on the selective reaction of the chain-end silanolate anion of living PDMS, with the silyl chloride function of 1, and subsequent linking reaction of the resulting ω-chain-end-benzyl chloride-functionalized polymer with either a living anionic polymer or living anionic block copolymer. With this methodology, various multiblock polymers containing PDMS blocks, up to the pentablock quintopolymer, were successfully synthesized. The second methodology using an α-phenylacrylate (PA reaction site was developed for the synthesis of multiblock polymers composed of all-vinyl polymer blocks. In this methodology, an α-chain-end-PA-functionalized polymer or block copolymer, via the living anionic polymerization, was first prepared and, then, reacted with appropriate living anionic polymer or block copolymer to link the two polymer chains. As a result, ACB (BCA, BAC (CAB, (ABn, (ACn, ABA, ACA, BCB, and ABCA multiblock polymers, where A, B, and C were polystyrene, poly(2-vinylpyridine, and poly(methyl methacrylate segments, could be successfully synthesized. The synthesis of triblock copolymers, BAB, CAC, and CBC, having molecular asymmetry in both side blocks, was also achieved. Furthermore, the use of living anionic polymers, derived from many other monomers, categorized as either of styrene, 2-vinylpyridine, or methyl methacrylate in monomer reactivity, in the linking methodology enabled the number of

  19. Bond Characteristics of Macro Polypropylene Fiber in Cementitious Composites Containing Nanosilica and Styrene Butadiene Latex Polymer

    Directory of Open Access Journals (Sweden)

    Jae-Woong Han


    Full Text Available This study evaluated the bond properties of polypropylene (PP fiber in plain cementitious composites (PCCs and styrene butadiene latex polymer cementitious composites (LCCs at different nanosilica contents. The bond tests were evaluated according to JCI SF-8, in which the contents of nanosilica in the cement were 0, 2, 4, 6, 8, and 10 wt%, based on cement weight. The addition of nanosilica significantly affected the bond properties between macro PP fiber and cementitious composites. For PCCs, the addition of 0–2 wt% nanosilica enhanced bond strength and interface toughness, whereas the addition of 4 wt% or more reduced bond strength and interface toughness. The bond strength and interfacial toughness of LCCs also increased with the addition of up to 6% nanosilica. The analysis of the relative bond strength showed that the addition of nanosilica affects the bond properties of both PCC and LCC. This result was confirmed via microstructural analysis of the macro PP fiber surface after the bond tests, which revealed an increase in scratches due to frictional forces and fiber tearing.

  20. Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

    KAUST Repository

    Karunakaran, Madhavan


    In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/ and 95% retention of PEG50K

  1. Mixed micellar nanoparticle of amphotericin B and poly styrene-block-poly ethylene oxide reduces nephrotoxicity but retains antifungal activity. (United States)

    Han, Kun; Miah, M A Jalil; Shanmugam, Srinivasan; Yong, Chul Soon; Choi, Han-Gon; Kim, Jung Ae; Yoo, Bong Kyu


    Mixed micellar nanoparticle consisting of amphotericin B (AmB) and poly styrene-block-poly ethylene oxide (PS-block-PEO) was prepared by high pressure homogenizer. Nephrotoxicity of the nanoparticle was investigated along with antifungal activity and self-aggregation status of the drug in the nanoparticle. Nephrotoxicity was markedly reduced when AmB was intravenously administered to rats as mixed micellar nanoparticle with PS-block-PEO in terms of transmission electron microscopy of tubular cells and creatinine clearance. Antifungal activity of AmB was not altered when the drug was in the form of mixed micellar nanoparticle compared to both conventional formulation and AmB micelle treated by same procedure without PS-block-PEO. Self-aggregation status of AmB molecules revealed monomeric in the mixed micellar nanoparticle with PS-block-PEO up to the therapeutic level of the drug (1-3 mM). The reduced nephrotoxicity of AmB in mixed micellar nanoparticle may be associated with the existence of the drug as monomeric form in the nanoparticle. Based on our result, formulation of AmB as mixed micellar nanoparticle with PS-block-PEO may be a promising alternative for the treatment of fungal diseases in patients who are at risk of renal dysfunction.

  2. Pyrolysis of waste electrical and electronic equipment: effect of antinomy trioxide on the pyrolysis of styrenic polymers. (United States)

    Hall, W J; Bhaskar, T; Merpati, N M M; Muto, A; Sakata, Y; Williams, P T


    This work has investigated the effect that antimony trioxide has on the pyrolysis of styrenic polymers and the effect that different types of brominated flame retardants used in plastics have on the composition of the pyrolysis products. Brominated high impact polystyrene (Br-HIPS) which contained either 5% or 0% antimony trioxide and either decabromodiphenyl oxide (DDO) or decabromodiphenyl ethane (DDE) was pyrolysed in a fixed bed reactor at 430 degrees C. Some experiments on the fixed bed reactor involved mixing the Br-HIPS with polystyrene. The gaseous products were analysed by GC-FID and GC-TCD and it was found that antimony trioxide caused an increase in the proportion of ethane and ethene and suppressed the proportion of butane and butene. When DDE was the flame retardant increased proportions of ethane and ethene were found in the pyrolysis gas compared to when DDO used. When polystyrene was mixed with the Br-HIPS it suppressed the trends observed in the gas composition during the pyrolysis of Br-HIPS. The pyrolysis oils were characterised using FT-IR, GC-MS, GC-FID, and GC-ECD. It was found that the plastic which did not contain antimony trioxide pyrolysed to form mainly toluene, ethylbenzene, styrene, cumene, and alpha-methylstyrene. The oils produced from the pyrolysis of the plastic that contained antimony trioxide did not contain any styrene or alpha-methylstyrene, but instead contained greater concentrations of ethylbenzene and cumene. The absence of styrene and alpha-methylstyrene from the pyrolysis oil occurred even when the Br-HIPS was mixed with polystyrene. GC-ECD analysis of the oils showed that the plastics which did not contain antimony trioxide pyrolysed to form (1-bromoethyl)benzene, which was totally absent from the pyrolysis oils when antimony trioxide was present in the plastic.

  3. Preparation and drug-loading properties of Fe{sub 3}O{sub 4}/Poly(styrene-co-acrylic acid) magnetic polymer nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Wensheng [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Coordination Chemistry Institute, School of Chemistry and Chemical Engineering and Life Science, Chaohu University, Chaohu 238000 (China); Shen, Yuhua, E-mail: [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Xie, Anjian [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Zhang, Weiqiang [School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Coordination Chemistry Institute, School of Chemistry and Chemical Engineering and Life Science, Chaohu University, Chaohu 238000 (China)


    Fe{sub 3}O{sub 4}/poly(styrene-co-acrylic acid) magnetic polymer nanocomposites were synthesized by the dispersion polymerization method using styrene as hard monomer, acrylic acid as functional monomer, Fe{sub 3}O{sub 4} nanoparticles modified with oleic acid as core, and poly(styrene-co-acrylic acid) as shell. Drug-loading properties of magnetic polymer nanocomposites with curcumin as a model drug were also studied. The results indicated that magnetic polymer nanocomposites with monodisperse were obtained, the particle size distribution was 50–120 nm, and the average size was about 100 nm. The contents of poly(styrene-co-acrylic acid) and Fe{sub 3}O{sub 4} nanoparticles in magnetic polymer nanocomposites were 74% and 24.7%, respectively. The drug-loading capacity and entrapment efficiency were 2.5% and 44.4%, respectively. The saturation magnetization of magnetic polymer nanocomposites at 300 K was 20.2 emu/g without coercivity and remanence. The as-prepared magnetic polymer nanocomposites have not only lots of functional carboxyl groups but also stronger magnetic response, which might have potential applications in drug carrier and targeted drug release.

  4. Nanostructured photovoltaic materials using block polymer assemblies (United States)

    Mastroianni, Sarah Elizabeth

    Despite its potential as an abundant, sustainable alternative to non-renewable energy sources, solar energy currently is underutilized. Photovoltaics, which convert energy from sunlight into electricity, commonly are made from inorganic semiconductor materials that require expensive manufacturing and processing techniques. Alternatively, organic materials can be used to produce flexible and lightweight organic photovoltaic (OPV) devices, which can be prepared using solution-based processing techniques. However, OPV devices are limited by low efficiencies and short lifetimes compared to their inorganic counterparts. In OPV systems, charge carriers are generated in the active layer via the separation of excitons (electron-hole pairs) at interfaces between donor and acceptor materials. Because excitons have a limited diffusion length (˜10 nm), they may recombine before reaching a donor-acceptor interface if domain sizes are large. This exciton recombination can limit device efficiency; thus, the design parameters for improved active layer morphologies include large interfacial areas, small size scales, and continuous conducting pathways. Currently, most OPV devices are prepared by blending donor and acceptor materials in bulk heterojunction (BHJ) devices, often resulting in non-ideal, process-dependent morphologies. Alternatively, the self-assembly of block polymers (BP)s offers a reproducible means to generate nanostructured active layers. The work presented in this dissertation examines the synthetic approaches to preparing BPs containing different electroactive materials: non-conjugated, amorphous poly(vinyl-m-triphenylamine) [PVmTPA] and conjugated poly(3-alkythiophene) [P3AT] p-type materials as well as fullerene-based n-type materials. The synthesis and self-assembly of a model poly(methyl methacrylate)- b-PVmTPA system is presented. This work was extended to synthesize PVmTPA BPs with complementary poly(methyl methacrylate- co-hydroxyethyl methacrylate) [P

  5. Transmission electron microscopy of polymer blends and block copolymers (United States)

    Gomez, Enrique Daniel

    -consistent field theory (SCFT). The liquid-like nature of this system at room temperature makes traditional staining methods for the enhancement of contrast ineffective. As an alternative, we take advantage of the large inelastic scattering cross-section of soft materials to generate contrast in zero-loss TEM images. Independent spatially resolved thickness measurements enable quantification of electron scattering. This enabled a comparison between the TEM data and predictions based on SCFT without any adjustable parameters. The second example involves the utilization of energy-filtered transmission electron microscopy (EFTEM) to compute elemental maps by taking advantage of ionization events. Elemental mapping of lithium is used to determine the distribution of salt in nanostructured poly(styrene-block-ethylene oxide) (SEO) copolymer/lithium salt electrolytes. Surprisingly, the concentration of lithium within a poly(ethylene oxide) (PEO) domain is found to be inhomogeneous; the salt is localized to the middle of the channels. Self-consistent field theory simulations suggest that localization of lithium is due to chain stretching at the interface, which increases with molecular weight. EFTEM and SCFT results show that the segregation of lithium salt to the middle of the PEO lamellae is greater for higher molecular weight polymers. This is correlated with the ionic conductivity of the copolymer electrolyte, which is found to show a higher conductivity for thinner lithium lamellae.

  6. Synthesis of carboxylated styrene polymer for internal calibration of Fourier transform ion cyclotron resonance mass-spectrometry of humic substances. (United States)

    Zherebker, Alexander; Turkova, Alexandra V; Kostyukevich, Yury; Kononikhin, Alexey; Zaitsev, Kirill V; Popov, Igor A; Nikolaev, Eugene; Perminova, Irina V


    We report synthesis and application of the novel carboxylated styrene for internal calibration of Fourier transform ion cyclotron resonance mass-spectra of humic substances. The calibrant was synthesized in five steps from acetylsalicylic acid (aspirin) followed by spontaneous polymerization of vinyl salicylic acid. Aromatic nature of the prepared polymer enabled its simultaneous analysis in the presence of the Suwannee River fulvic acid without using dual-spray approach. The major advantage of the calibrant proposed in this study is a lack of suppression of humic substances signals and maintenance of peak intensity distribution. The appropriate calibration resulted in an increased number of unambiguous identification in Suwannee River fulvic acid. Thanks to the higher mass accuracy, it was also possible to refine attribution of the CHOS species to hydrolysable tannins as opposed to the erroneous previous assignment to the condensed tannins.

  7. Wood-polymer composite: physical and mechanical properties of some wood species impregnated with styrene and methyl methacrylate

    Directory of Open Access Journals (Sweden)

    Denise Ortigosa Stolf


    Full Text Available This study aimed to demonstrate the feasibility of obtaining wood-polymer composites (WPC displaying a performance superior to that of untreated wood from reforested genera. To this end, wood samples of Pine (Pinus caribaea and Eucalyptus (Eucalyptus grandis, whose density is compatible with this process, were impregnated with the polymeric monomers styrene and methyl methacrylate, using benzoyl peroxide to initiate the polymerization process forming free radicals. The vacuum-pressure method was used to impregnate the samples with monomer-initiator solution. The results indicated a significant improvement of all the properties investigated, including dimensional stability, for the Pine-WPC, while Eucalyptus-WPC, owing to the wood's low permeability, showed only increased values of hardness parallel and perpendicular to grain.

  8. Star polymers by ATRP of styrene and acrylates employing multifunctional initiators

    DEFF Research Database (Denmark)

    Jankova, Katja Atanassova; Bednarek, Melania; Hvilsted, Søren


    Multifunctional initiators for atom transfer radical polymerization (ATRP) are prepared by converting ditrimethylolpropane with four hydroxyl groups, dipentaerythritol with six hydroxyl groups, and poly(3-ethyl-3-hydroxymethyl-oxetane) with similar to 11 hydroxyl groups to the corresponding 2......-bromoisobutyrates or 2-bromopropionates as obtained by reaction with acid bromides. Star polystyrene (PS) is produced by using these macroinitiators and neat styrene in a controlled manner by ATRP at 110 degrees C, employing the catalytic system CuBr and bipyridine. M. up to 51,000 associated with narrow molecular...

  9. Novel Electroactive Polymers and Block Copolymers (United States)


    state cells , active component in sensors. photoelectrochemnical displays and ultrathin membranes between an electrode and a polymer electrolytes in a...solid state cell . Solvent free sensors require a microelectrode/thin ionic media combination. In the solid state morphology depicted in Figure 1, the...electron conducting microdomain will act as a micro/ nanoelectrode in excellent contact with the surrounding ionc media. Therefore, any small changes in

  10. Magnetic and dielectric properties of sulfonated (S) poly[(styrene)-(ethylene-co-butylene)]-styrene (SEBS) block copolymer/magnetic metal oxide nanocomposites synthesized via an in-situ precipitation method (United States)

    Peddini, Sateesh Kumar

    Block copolymer/magnetic metal oxide nanocomposites were synthesized by growing metal oxide nanoparticles (cobalt ferrite, CoFe2O 4 and iron oxide, alpha-Fe2O3) in sulfonated (s) poly (styrene) (PS) block domains of sulfonated poly [(styrene)-(ethylene-co-butylene)-(styrene)] (SEBS) BCP preformed films via an in-situ precipitation method by dissolving the salts of respective metal chloride (s) in a suitable solvent that selectively swells the sPS regions. Inorganic uptake was determined using thermogravimetric analysis (TGA), and it was observed that none of the samples incorporated more than 5 wt % of the inorganic component. Dynamical mechanical analysis was used to observe the changes in the glass transition temperatures (T g) in both blocks of the BCP by plotting tan delta vs. temperature responses in tensile mode on all samples. The results showed that the T g of the sPS block domains increased with sulfonation level and further increased with the incorporation of both nanoparticles in the same blocks, indicating that growth of nanoparticles takes place only in sPS blocks. The crystalline structure of the nanoparticles was observed using wide angle X-ray diffractometry (WAXD), and it was determined that cobalt iron oxide nanoparticles in 20 mole % sulfonated SEBS exhibited an inverse spinel structure confirming the structure to be CoFe2O4. And with iron oxide nanoparticles in 10 mole % sulfonated SEBS exhibiting a hematite (alpha-Fe2O 3) phase. Transmission electron microscopy (TEM) was used to investigate the particle size and distribution of nanoparticles in sBCP matrices at all sulfonation levels. Select area electron diffraction in TEM was used to determine crystalline structures of individual nanoparticles to compare with the structure observed from WAXD. The changes in thickness of interfaces between the individual PS and EB block domains with increase in sulfonation of PS blocks were investigated semi-quantitatively using tapping mode atomic force

  11. Transparent Wood Smart Windows: Polymer Electrochromic Devices Based on Poly(3,4-Ethylenedioxythiophene):Poly(Styrene Sulfonate) Electrodes. (United States)

    Lang, Augustus W; Li, Yuanyuan; De Keersmaecker, Michel; Shen, D Eric; Österholm, Anna M; Berglund, Lars; Reynolds, John R


    Transparent wood composites, with their high strength and toughness, thermal insulation, and excellent transmissivity, offer a route to replace glass for diffusely transmitting windows. Here, conjugated-polymer-based electrochromic devices (ECDs) that switch on-demand are demonstrated using transparent wood coated with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a transparent conducting electrode. These ECDs exhibit a vibrant magenta-to-clear color change that results from a remarkably colorless bleached state. Furthermore, they require low energy and power inputs of 3 mWh m-2 at 2 W m-2 to switch due to a high coloration efficiency (590 cm2  C-1 ) and low driving voltage (0.8 V). Each device component is processed with high-throughput methods, which highlights the opportunity to apply this approach to fabricate mechanically robust, energy-efficient smart windows on a large scale. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Penelitian “polymer blend” high styrene rubber dengan karet alam untuk “sponnge middle sole”

    Directory of Open Access Journals (Sweden)

    Penny Setyowati


    Full Text Available The objective of this research was find optimum composision of polymer blend of High Styrene Rubber (HSR and Natural Rubber (SIR 3L for preparation sponge middle sole that save the best fisical properties, strong, flexible, light, stable and thermoplastic properties. The formulation of rubber compound has to be researched as much as 3 formalition MS 1, MS II and MS III with variation of SIR 3L, HSR and HAF black as follows, MS I 70-30-20 phr ; MS II 80-20-30 PHR and MS III 90-10-40 phr . From the fisical test analysis, optimum formulation to be reached at the compound formualtion MS III with result of fisical test as follows : Tensile strength : 0.572 kg/mm2 ; Elongation at break : 204% ; Hardness share A : 55,8 : Density 0,728 gr/cm3 : Tear Resistance : 0,296 kg/mm2 and Compression Set 22,042%.

  13. Polymer composites prepared from heat-treated starch and styrene-butadiene latex (United States)

    Thermoplastic starch/latex polymer composites were prepared using styrene–butadiene (SB) latex and heat-treated cornstarch. The composites were prepared in a compression mold at 130 °C, with starch content 20%. An amylose-free cornstarch, waxy maize, was used for this research and the heat treatment...

  14. Shape Memory Polymer Composites of Poly(styrene-b-butadiene-b-styrene Copolymer/Liner Low Density Polyethylene/Fe3O4 Nanoparticles for Remote Activation

    Directory of Open Access Journals (Sweden)

    Yongkun Wang


    Full Text Available Magnetically sensitive shape memory poly(styrene-b-butadiene-b-styrene copolymer (SBS/liner low density polyethylene (LLDPE composites filled with various contents of Fe3O4 nanoparticles were prepared. The influence of the Fe3O4 nanoparticles content on the thermal properties, mechanical properties, fracture morphology, magnetic behavior, and shape memory effect of SBS/LLDPE/Fe3O4 composites was systematically studied in this paper. The results indicated that homogeneously dispersed Fe3O4 nanoparticles ensured the uniform heat generation and transfer in the alternating magnetic field, and endowed the SBS/LLDPE/Fe3O4 composites with an excellent magnetically responsive shape memory effect. When the shape memory composites were in the alternating magnetic field (f = 60 kHz, H = 21.21 kA·m−1, the best shape recovery ratio reached 99%, the shape retention ratio reached 99.4%, and the shape recovery speed increased significantly with the increment of Fe3O4 nanoparticles. It is anticipated that tagging products with this novel shape memory composite is helpful for the purpose of an intravascular delivery system in Micro-Electro-Mechanical System (MEMS devices.


    Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NSynthesis and characterization of sulfonated polymers for ionomeric membranes based on styrene copolymers; Sintese e caracterizacao de precursores sulfonados para membranas polimericas a base de copolimeros estirenicos

    Energy Technology Data Exchange (ETDEWEB)

    Becker, C.M.; Forte, M.M.C.; Amico, S.C. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia. Lab. de Materiais Polimericos (LAPOL)], e-mail:, e-mail:, e-mail:; Vargas, J.V.C. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica], e-mail:


    Polymer electrolyte membrane fuel cell (PEMFC) have emerged strongly as a viable alternative for power source owing to their high energy efficiency and environmental friendliness. Currently, Nafion is the most frequently used membrane even though it has a high cost. The objective of this work is to synthesize sulfonated polymers, based on styrene copolymers, with different sulfonation degrees as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the resulting polymers were characterized by Fourier Transform Infra-red (FTIR), thermogravimetric analysis (TGA) and degree of substitution or sulfonation (DS). The polyelectrolytes were evaluated regarding their ion exchange capacity (IEC) and conductivity. The results demonstrated that increasing the sulfonic acid content of the polymer results in higher IEC, conductivity and water uptake. (author)

  16. Low Work-function Poly(3,4-ethylenedioxylenethiophene): Poly(styrene sulfonate) as Electron-transport Layer for High-efficient and Stable Polymer Solar Cells


    Yong Zhang; Lie Chen; Xiaotian Hu; Lin Zhang,; Yiwang Chen


    Low-work-function poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) modified with polyethylenimine (PEIE) was used as an electron transport layer (ETL) for polymer solar cells (PSCs). A thin layer of PEIE film was spin-coated onto the surface on the PEDOT:PSS films, thus substantially changing their charge selectivity from supporting hole transport to supporting electron transport. It was also found that the PEDOT:PSS/PEIE ETL exhibited higher interfacial contact, a more fa...

  17. New insights into the effects of styrene-butadiene-styrene polymer modifier on the structure, properties, and performance of asphalt binder: The case of AP-5 asphalt and solvent deasphalting pitch

    Energy Technology Data Exchange (ETDEWEB)

    Nciri, Nader, E-mail: [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Kim, Namho [Department of Architectural Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Cho, Namjun, E-mail: [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of)


    This paper deals with the poorly understood effects of styrene-butadiene-styrene (SBS) copolymer on the bitumen performance. It focuses on determining the impact of various concentrations (e.g., 0, 4, 8, and 12 wt. %) of SBS on the attributes of two types of asphalt namely AP-5 asphalt and solvent deasphalting (SDA) pitch. The unmodified and modified binders were investigated in terms of their chemical compositions, microstructures, thermo-analytical behaviors, and physical properties. The intricate chemical compositions were evaluated by elemental analysis and thin layer chromatography-ionization detection (TLC-FID). Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron microscopy (SEM), and X-ray diffraction (XRD) were utilized to examine the microstructures. Whereas, thermal characteristics were evaluated by thermogravimetric analysis (TGA/DTGA) and differential scanning calorimetry (DSC). The physical behaviors were monitored through the softening point, penetration, viscosity, and ductility tests. The findings showed that the blending of asphalt with different amounts of SBS resulted into different rheological behaviors. This was reflected from the difference in the SARA (i.e., saturates, aromatics, resins, and asphaltenes) compositions and colloidal instability indexes of the modified asphalts. SEM exhibited a continuous asphalt phase with distributed SBS particles, a continuous polymer phase with distributed asphalt globules, or two interconnected continuous phases. FT-IR, {sup 1}H {sup 13}C NMR, and XRD data revealed that the AP-5 asphalt and SDA pitch experienced a number of distinct structural changes. TGA/DSC studies determined the occurrence of diverse events during thermal treatment. It is concluded that the degree of SBS modification depends strongly on SARA composition and polymer content. If the polymers are molded at higher concentrations along with aromatics-rich SDA pitches, then the mixtures

  18. Unexpected differences between thermal and photoinitiated cationic curing of a diglycidyl ether of bisphenol A modified with a multiarm star poly(styrene-b-poly(ε-caprolactone polymer

    Directory of Open Access Journals (Sweden)

    J. M. Morancho


    Full Text Available The effect of adding a multiarm star poly(styrene-b-poly(ε-caprolactone polymer on the cationic thermal and photoinitiated curing of diglycidyl ether of bisphenol A was studied. This star-polymer decelerated the thermal curing of diglycidyl ether of bisphenol A and modified the final structure of the epoxy matrix. The photocuring was influenced significantly by the addition of the multiarm star. When the proportion of this modifier added was 5%, much more time was necessary for complete photocuring (160 min at 40ºC. In the presence of 10% of modifier, the degree of photocuring reached was very low (0.196 at 120°C. A subsequent thermal post-curing was necessary to cure completely the system. During photocuring in presence of poly(styrene-b-poly(ε-caprolactone, the formation of dormant species, which are reactivated when the temperature increases, takes places. The kinetics of the thermal curing and the photocuring was analyzed using an isoconversional method due to the complexity of the reactive process. Applying this method, it has been confirmed the dependence of activation energy on the degree of conversion. The fracture morphology analyzed by scanning electron microscopy exhibited a second phase originated during photocuring by the presence of the modifier.

  19. Blocked Shape Memory Effect in Negative Poisson's Ratio Polymer Metamaterials. (United States)

    Boba, Katarzyna; Bianchi, Matteo; McCombe, Greg; Gatt, Ruben; Griffin, Anselm C; Richardson, Robert M; Scarpa, Fabrizio; Hamerton, Ian; Grima, Joseph N


    We describe a new class of negative Poisson's ratio (NPR) open cell PU-PE foams produced by blocking the shape memory effect in the polymer. Contrary to classical NPR open cell thermoset and thermoplastic foams that return to their auxetic phase after reheating (and therefore limit their use in technological applications), this new class of cellular solids has a permanent negative Poisson's ratio behavior, generated through multiple shape memory (mSM) treatments that lead to a fixity of the topology of the cell foam. The mSM-NPR foams have Poisson's ratio values similar to the auxetic foams prior their return to the conventional phase, but compressive stress-strain curves similar to the ones of conventional foams. The results show that by manipulating the shape memory effect in polymer microstructures it is possible to obtain new classes of materials with unusual deformation mechanisms.

  1. 78 FR 6213 - Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption AGENCY: Environmental...; also known as styrene-2-ethylhexyl acrylate copolymer when used as an inert ingredient in a pesticide...-risk polymers are described in 40 CFR 723.250(d). Styrene-2-ethylhexyl acrylate copolymer conforms to...

  2. Self-Assembly of Block Copolymer Chains To Promote the Dispersion of Nanoparticles in Polymer Nanocomposites. (United States)

    Liu, Jun; Wang, Zixuan; Zhang, Zhiyu; Shen, Jianxiang; Chen, Yulong; Zheng, Zijian; Zhang, Liqun; Lyulin, Alexey V


    In this paper we adopt molecular dynamics simulations to study the amphiphilic AB block copolymer (BCP) mediated nanoparticle (NP) dispersion in polymer nanocomposites (PNCs), with the A-block being compatible with the NPs and the B-block being miscible with the polymer matrix. The effects of the number and components of BCP, as well as the interaction strength between A-block and NPs on the spatial organization of NPs, are explored. We find that the increase of the fraction of the A-block brings different dispersion effect to NPs than that of B-block. We also find that the best dispersion state of the NPs occurs in the case of a moderate interaction strength between the A-block and the NPs. Meanwhile, the stress-strain behavior is probed. Our simulation results verify that adopting BCP is an effective way to adjust the dispersion of NPs in the polymer matrix, further to manipulate the mechanical properties.

  3. DMFC Performance of Polymer Electrolyte Membranes Prepared from a Graft-Copolymer Consisting of a Polysulfone Main Chain and Styrene Sulfonic Acid Side Chains

    Directory of Open Access Journals (Sweden)

    Nobutaka Endo


    Full Text Available Polymer electrolyte membranes (PEMs for direct methanol fuel cell (DMFC applications were prepared from a graft-copolymer (PSF-g-PSSA consisting of a polysulfone (PSF main chain and poly(styrene sulfonic acid (PSSA side chains with various average distances between side chains (Lav and side chain lengths (Lsc. The polymers were synthesized by grafting ethyl p-styrenesulfonate (EtSS on macro-initiators of chloromethylated polysulfone with different contents of chloromethyl (CM groups, and by changing EtSS content in the copolymers by using atom transfer radical polymerization (ATRP. The DMFC performance tests using membrane electrode assemblis (MEAs with the three types of the PEMs revealed that: a PSF-g-PSSA PEM (SF-6 prepared from a graft copolymer with short average distances between side chains (Lav and medium Lsc had higher DMFC performance than PEMs with long Lav and long Lsc or with short Lav and short Lsc. SF-6 had about two times higher PDmax (68.4 mW/cm2 than Nafion® 112 at 30 wt % of methanol concentration. Furthermore, it had 58.2 mW/cm2 of PDmax at 50 wt % of methanol concentration because of it has the highest proton selectivity during DMFC operation of all the PSF-g-PSSA PEMs and Nafion® 112.

  4. Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Tzu-Pin [Division; Chang, Alice B. [Division; Luo, Shao-Xiong [Division; Chen, Hsiang-Yun [Division; Lee, Byeongdu [X-Ray; Grubbs, Robert H. [Division


    Grafting density is an important structural parameter that imparts significant influences over the physical properties of architecturally complex polymers. In this report, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymer-ization (ROMP). ω-norbornenyl poly(D,L-lactide) (PLA) and polystyrene (PS) macromonomers were copolymerized with discrete co-monomers in different feed ratios, enabling precise control over the grafting density. Small-angle X-ray scattering (SAXS) experiments demonstrate that these graft block polymers can self-assemble into long-range-ordered lamellar structures. For seventeen series of block polymers with variable z, the scal-ing of the lamellar period with the total backbone degree of polymerization (d* ~ Nbbα) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, instead of segregation strengths. A model is pro-posed in which the characteristic ratio (C∞), a proxy for the backbone stiffness, scales with Nbb as a function of the grafting density: C ~ Nbbf(z). To the best of our knowledge, this report represents the first study of scaling behavior for the self-assembly of block polymers with variable grafting density. The relationships disclosed herein provide valuable insights into conformational changes with grafting density, thus introducing new opportunities for future block polymer design.

  5. Inorganic-organic hybrid polymer electrolyte based on polysiloxane/poly(maleic imide-co-styrene) network

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, P.-L.; Jheng, W.-H.; Chen, W.-F. [Department of Chemical Engineering, National Cheng Kung University, Tainan City 70101 (China); Liang, W.-J. [Fire Protection and Safety Research Center, National Cheng Kung University, Tainan City (China)


    Covalently cross-linked nonfluorinated hydrocarbon ionomers are synthesized by introducing sulfonate groups and a siloxane cross-linker through thermally and chemically stable imide bonding on poly(styrene-co-maleic anhydride). The three-dimensional polysiloxane framework, which does not only act as a robust scaffold but also provide sites for the hydrogen bonding with water, contribute to the increase in bound water degree, higher proton conductivity at lower ion exchange capacity, and greatly decreased methanol permeability. The spherical-shaped ionic clusters produce a comparable proton conductivity (10{sup -1} S cm{sup -1} above 60 C) to Nafion-117. The conductivity of the hybrid ionomer does not decrease to gain its selectivity, but instead increased. Methanol permeability is {proportional_to}70% lower than that of Nafion-117, but has a higher water uptake and IEC. The membrane with IEC values of 1.1 mequiv. g{sup -1} exhibits a constant conductivity for 200 h in hydrolytic stability test, and produce a power density 20% higher than Nafion-117 in single DMFC operation. (author)

  6. Low Work-function Poly(3,4-ethylenedioxylenethiophene): Poly(styrene sulfonate) as Electron-transport Layer for High-efficient and Stable Polymer Solar Cells (United States)

    Zhang, Yong; Chen, Lie; Hu, Xiaotian; Zhang, Lin; Chen, Yiwang


    Low-work-function poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) modified with polyethylenimine (PEIE) was used as an electron transport layer (ETL) for polymer solar cells (PSCs). A thin layer of PEIE film was spin-coated onto the surface on the PEDOT:PSS films, thus substantially changing their charge selectivity from supporting hole transport to supporting electron transport. It was also found that the PEDOT:PSS/PEIE ETL exhibited higher interfacial contact, a more favorable active morphology, and improved charge mobility. By virtue of these beneficial properties, inverted PSCs based on low-bandgap semiconducting photoactive layers achieved a notably improved power conversion efficiency (PCE) of 7.94%, superior even to the corresponding performance of devices with only a ZnO layer. Surpassing our expectations, compared with the extreme degradation of device stability observed when pure PEDOT:PSS is used, PEIE-modified PEDOT:PSS can considerably suppress device degradation because of the hydrophobic and alkaline nature of PEIE, which not only reduces the hygroscopicity of the PEDOT:PSS but also neutralizes the acidic PEDOT:PSS and thus prevents the corrosion of the ITO cathode. These results demonstrate the potential of PEIE-modified PEDOT:PSS for use as an efficient ETL in commercial printed electronic devices.

  7. Removal of Copper ions from aqueous solutions using polymer derivations of poly (styrene-alt-maleic anhydride

    Directory of Open Access Journals (Sweden)

    Naser Samadi


    Full Text Available In this study chelating resins have been considered to be suitable materials for the recovery of Copper (II ions in water treatments. Furthermore, these modified resins were reacted with 1,2-diaminoethane in the presence of ultrasonic irradiation for the preparation of a tridimensional chelating resin on the Nano scale for the recovery of Copper (II ions from aqueous solutions. This method which is used for removing and determining Copper (II ions using copolymers derived resins of poly (styrene-alternative-maleic anhydride (SMA and atomic absorption spectroscopy. The method is simple, sensitive, inexpensive and fast. The various parameters such as pH, contact time, concentrations of metal ions, mass of resin, and agitation speed were investigated on adsorption effect. The adsorption behavior of Copper (II ions were investigated by the synthesis of chelating resins at various pHs. The prepared resins showed a good tendency for removing the selected metal ions from aqueous solution, even at an acidic pH. Also, the prepared resins were examined for the removal of Copper (II ions from real samples such as industrial wastewater and were shown to be very efficient at adsorption in the cases of Copper (II ions. The pseudo-first-order, pseudo-second-order, and intra-particle diffusion kinetics equations were used for modeling of adsorption data and it was shown that pseudo-second-order kinetic equation could best describe the adsorption kinetics. The intra-particle diffusion study revealed that external diffusion might be involved in this case. The resins were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis.

  8. Effect of block composition on thermal properties and melt viscosity of poly[2-(dimethylaminoethyl methacrylate], poly(ethylene oxide and poly(propylene oxide block co-polymers

    Directory of Open Access Journals (Sweden)


    Full Text Available To modify the rheological properties of certain commercial polymers, a set of block copolymers were synthesized through oxyanionic polymerization of 2-(dimethylaminoethyl methacrylate to the chain ends of commercial prepolymers, namely poly(ethylene oxide (PEO, poly(ethylene oxide-block-poly(propylene oxide-block-poly(ethylene oxide (PEO-PPO-PEO, and poly(propylene oxide (PPO. The formed block copolymers were analysed with size exclusion chromatography and nuclear magnetic resonance spectroscopy in order to confirm block formation. Thermal characterization of the resulting polymers was done with differential scanning calorimetry. Thermal transition points were also confirmed with rotational rheometry, which was primarily used to measure melt strength properties of the resulting block co-polymers. It was observed that the synthesised poly[2-(dimethylaminoethyl methacrylate]-block (PDM affected slightly the thermal transition points of crystalline PEO-block but the influence was stronger on amorphous PPO-blocks. Frequency sweeps measured above the melting temperatures for the materials confirmed that the pre-polymers (PEO and PEO-PPO-PEO behave as Newtonian fluids whereas polymers with a PDM block structure exhibit clear shear thinning behaviour. In addition, the PDM block increased the melt viscosity when compared with that one of the pre-polymer. As a final result, it became obvious that pre-polymers modified with PDM were in entangled form, in the melted state as well in the solidified form.

  9. Control of Directed Self-Assembly in Block Polymers by Polymeric Topcoats

    Energy Technology Data Exchange (ETDEWEB)

    Ramírez-Hernández, Abelardo; Suh, Hyo Seon; Nealey, Paul F.; de Pablo, Juan J.


    The morphology of a block copolymer thin film is particularly sensitive to its boundary conditions. Lithographic applications of block polymers in the microelectronics and memory device industries require formation of morphologies with perpendicularly oriented domains. Current fabrication targets envisage the creation of dense arrays of structures with domain sizes in the sub-10 nanometer regime. Such length scales can be reached by resorting to block polymers with highly incompatible blocks (and a large Flory-Huggings parameter, x). High-x values, however, generally lead to large differences in the surface energies of the corresponding blocks, thereby interfering with formation of the sought after perpendicularly oriented domains. In this work, a theoretically informed coarse grain model is used to introduce a topcoat strategy that enables control of the orientation of block copolymer domains in highly incompatible block polymer materials. A systematic study of a wide range of polymeric material combinations is presented, and the conditions leading to optimal assembly of perpendicular morphologies are clearly identified. We consider the effect of molecular weight, block polymer film thickness and architecture, and degree of incompatibility. Our results are summarized in the form of generic phase diagrams that should serve as a guide for experimental deployment of the top-coat strategy put forth in this work.

  10. Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush. (United States)

    Lin, Tzu-Pin; Chang, Alice B; Luo, Shao-Xiong; Chen, Hsiang-Yun; Lee, Byeongdu; Grubbs, Robert H


    Grafting density is an important structural parameter that exerts significant influences over the physical properties of architecturally complex polymers. In this report, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization. ω-Norbornenyl poly(d,l-lactide) and polystyrene macromonomers were copolymerized with discrete comonomers in different feed ratios, enabling precise control over both the grafting density and molecular weight. Small-angle X-ray scattering experiments demonstrate that these graft block polymers self-assemble into long-range-ordered lamellar structures. For 17 series of block polymers with variable z, the scaling of the lamellar period with the total backbone degree of polymerization (d* ∼ Nbbα) was studied. The scaling exponent α monotonically decreases with decreasing z and exhibits an apparent transition at z ≈ 0.2, suggesting significant changes in the chain conformations. Comparison of two block polymer systems, one that is strongly segregated for all z (System I) and one that experiences weak segregation at low z (System II), indicates that the observed trends are primarily caused by the polymer architectures, not segregation effects. A model is proposed in which the characteristic ratio (C∞), a proxy for the backbone stiffness, scales with Nbb as a function of the grafting density: C∞ ∼ Nbbf(z). The scaling behavior disclosed herein provides valuable insights into conformational changes with grafting density, thus introducing opportunities for block polymer and material design.

  11. Microtome Sliced Block Copolymers and Nanoporous Polymers as Masks for Nanolithography

    DEFF Research Database (Denmark)

    Shvets, Violetta; Schulte, Lars; Ndoni, Sokol


    Introduction. Block copolymers self-assembling properties are commonly used for creation of very fine nanostructures [1]. Goal of our project is to test new methods of the block-copolymer lithography mask preparation: macroscopic pieces of block-copolymers or nanoporous polymers with cross......-b-PDMS) of different morphologies with period of structure ~24nm [2]. It was shown that mechanical shear-alignment of cylindrical block copolymer with PDMS cylinders in PB matrix orients cylinders in the direction of shearing. Subsequently PB is cross-linked by dicumyl peroxide to fix cylinder orientation. Afterwards...

  12. Semiconducting Polymer Photodetectors with Electron and Hole Blocking Layers: High Detectivity in the Near-Infrared

    Directory of Open Access Journals (Sweden)

    Xiong Gong


    Full Text Available Sensing from the ultraviolet-visible to the infrared is critical for a variety of industrial and scientific applications. Photodetectors with broad spectral response, from 300 nm to 1,100 nm, were fabricated using a narrow-band gap semiconducting polymer blended with a fullerene derivative. By using both an electron-blocking layer and a hole-blocking layer, the polymer photodetectors, operating at room temperature, exhibited calculated detectivities greater than 1013 cm Hz1/2/W over entire spectral range with linear dynamic range approximately 130 dB. The performance is comparable to or even better than Si photodetectors.

  13. Side chain alkylation of toluene with methanol over basic zeolites - novel production route towards styrene?

    NARCIS (Netherlands)

    Rep, M.; Rep, M.


    Styrene is an important monomer for the production of different types of (co-) polymers that are used in, e.g., toys, medical devices, food packaging, paper coatings etc. Styrene is produced with several different industrial processes. In 1998, the production of styrene monomer was approximately 21

  14. Styrene polymerization in three-component cationic microemulsions

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Luna, V.H.; Puig, J.E. (Universidad de Guadalajara (Mexico)); Castano, V.M. (Instituto de Fisica (Mexico)); Rodriguez, B.E.; Murthy, A.K.; Kaler, E.W. (Univ. of Delaware, Newark (USA))


    The polymerization of styrene in three-component dodecyltrimethylammonium bromide (DTAB) microemulsions is reported. The structure of the unpolymerized microemulsions, determined by conductimetry and quasielastic light scattering (QLS), is consistent with styrene-swollen micelles in equilibrium with regular micelles, both dispersed in an aqueous phase. Polymerization of these transparent microemulsions, monitored by QLS an dilatometry, produced stable, bluish monodisperse microlatices with particle radii ranging from 20 to 30 nm, depending on styrene content. Polymerization initiation appears to occur in the styrene-swollen micelles, and the polymer particles grow by recruiting monomer and surfactant from uninitiated droplets and small micelles.

  15. Di-block co-polymer derived nanoporous polymer liquid core waveguides

    DEFF Research Database (Denmark)

    Christiansen, Mads Brøkner; Gopalakrishnan, Nimi; Sagar, Kaushal Shashikant


    Nanoporous liquid core waveguides are fabricated by selectively UV modifying a nanoporous polymer. The starting point is a diblock polymer where 1,2-polybutadiene (PB) molecules are bound to PDMS. When the PB is cross linked it self-assembles into PB with a network of 14 nm diameter PDMS filled p...

  16. Synthesis of Coordination Polymer Nanoparticles using Self-Assembled Block Copolymers as Template. (United States)

    Weber, Birgit


    Nowadays there is a high demand in specialized functional materials, for example, for applications as sensors in biomedicine. For the realization of such applications, nanostructures and the integration in a composite matrix are indispensable. Coordination polymers and networks, for example, with spin crossover properties, are a highly promising family of switchable materials in which the switching process can be triggered by various external stimuli. An overview over different strategies for the synthesis of nanoparticles of such systems is given. A special focus is set on the use of block copolymer micelles as templates for the synthesis of nanocomposites. The block copolymer defines the final size and shape of the nanoparticle core. Additionally it allows a further functionalization of the obtained nanoparticles by variation of the polymer blocks and an easy deposition of the composite material on surfaces. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Structure of poly(styrene-b-ethylene-alt-propylene) diblock copolymer micelles in squalane. (United States)

    Choi, Soo-Hyung; Bates, Frank S; Lodge, Timothy P


    The temperature dependence of the micellar structures formed by poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers in squalane, a highly selective solvent for the PEP blocks, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Four SEP diblock copolymers were prepared by sequential anionic polymerization of styrene and isoprene, followed by hydrogenation of the isoprene blocks, to yield SEP(17-73), SEP(26-66), SEP(36-69), and SEP(42-60), where the numbers indicate block molecular weights in kDa. All four polymers formed well-defined spherical micelles. In dilute solution, DLS provided the temperature-dependent mean hydrodynamic radius, R(h), and its distribution, while detailed fitting of the SAXS profiles gave the core radius, R(c), the equivalent hard sphere radius, R(hs), and an estimate of the aggregation number, N(agg). In general, the micelles became smaller as the critical micelle temperature (CMT) was approached, which was well above the glass transition of the core block. As concentration increased the micelles packed onto body centered cubic lattices for all four copolymers, which underwent order-disorder transitions upon heating near the dilute solution CMTs. The results are discussed in terms of current understanding of block copolymer solution self-assembly, and particular attention is paid to the issue of equilibration, given the high glass transition temperature of the core block.


    Directory of Open Access Journals (Sweden)

    A. V. Firsova


    Full Text Available The article discusses the use of organomagnesium initiators in the synthesis of styrene-butadiene random copolymer (SBR obtained solution polymerization and their influence on the properties of rubber. Selected organic magnesium dialkyl initiator is combined with a modifier, which is a mixed alkoxide of an alkali and alkaline earth metals, which allows to control the micr ostructure of the diene polymer and its molecular weight characteristics. Alcohol derivatives selected high-boiling alcohols tetra (hydroxypropyl ethylenediamine (lapromol 294 and tetrahydrofurfuryl alcohol (TGFS. Selection of high-boiling alcohols due to the fact that the destruction of alkoxide with aqueous polymer degassing they do not fall into the return solvent and almost fall into the exact water. The metal components of alkoxides are lithium, sodium, potassium, magnesium and calcium. The resulting solutions are stable when stored modifier t hroughout the year even at -40 °C. The scheme of obtaining the new catalyst systems based organomagnesium and alcoxide of alkali and alkaline earth metals, which yields as functionalized SBR with a statistical and a distribution block of butadiene and styrene was developed. The process of copolymerization with styrene to butadiene organomagnesium initiators as using an organolithium compound (n-butyllithium was carried out, and without it. Found that the addition of n-butyllithium in the reaction mixture leads to a sharp increase in the rate of reaction. The results of studies of the effect of composition of the initiator system on the structure of diene polymers. It was revealed that a mixed initiator system affords a high conversion of monomers (to 90 % in 1 hour 1,2-polybutadiene content increased to 60 %. The process of polymerization of only a mixture of organomagnesium initiators and alcoxide of alkali and alkaline earth metals are not actively proceeds, conversion of the monomers reaches to 90 % in 4 hours, the microstructure

  19. Polymer-Block-Polypeptides and Polymer-Conjugated Hybrid Materials as Stimuli-Responsive Nanocarriers for Biomedical Applications. (United States)

    John, Johnson V; Johnson, Renjith P; Heo, Min Seon; Moon, Byeong Kyu; Byeon, Seong Jin; Kim, Il


    Stimuli-responsive nanocarriers are a class of soft materials that includes natural polymers, synthetic polymers, and polypeptides. Recently, modern synthesis tools such as atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, nitroxide-mediated radical polymerization, ring-opening polymerization of α-amino acid N-carboxyanhydrides, and various "click" chemistry strategies were simultaneously employed for the design and synthesis of nanosized drug delivery vehicles. Importantly, the research focused on the improvement of the nanocarrier targetability and the site-specific, triggered release of therapeutics with high drug loading efficiency and minimal drug leakage during the delivery to specific targets. In this context, nanocarriers responsive to common stimuli such as pH, temperature, redox potential, light, etc. have been widely used for the controlled delivery of therapeutics to pathological sites. Currently, different synthesis and self-assembly strategies improved the drug loading efficacy and targeted delivery of therapeutic agents to the desired site. In particular, polypeptide-containing hybrid materials have been developed for the controlled delivery of therapeutic agents. Therefore, stimuli-sensitive synthetic polypeptide-based materials have been extensively investigated in recent years. This review focuses on recent advances in the development of polymer-block-polypeptides and polymer-conjugated hybrid materials that have been designed and evaluated for various stimuli-responsive drug and gene delivery applications.

  20. Platform Approach to Produce Polymer Nanoparticles with Modular Functionality from Amphiphilic Block Copolymer Stabilizers (United States)


    block weight percentages for all BCPs are in the range of 75 to 85 wt%. Furthermore, the calculated hydrophilic-lipophilic balance ( HLB ) for each...polymer resides in the range of 14‒16. HLB values greater than 12 are predicted to stabilize oil-in-water emulsions.21 Table 1. Synthesized BCPs...light scattering DMF dimethylformamide DMSO dimethyl sulfoxide EO ethylene oxide FTIR HLB Fourier transform infrared spectroscopy hydrophilic

  1. Comparison of sodium naphthenate and air-ionization corona discharge as surface treatments for the ethylene-tetrafluoroethylene polymer (ETFE) to improve adhesion between ETFE and acrylonitrile-butadiene-styrene polymer (ABS) in the presence of a cyanoacrylate adhesive (CAA) (United States)

    Lucía Johanning-Solís, Ana; Stradi-Granados, Benito A.


    This study compares two ethylene-tetrafluoroethylene (ETFE) surface activation treatments, namely chemical attack with a solution of sodium naphthenate and plasma erosion via air-ionization corona discharge in order to improve the adhesive properties of the ETFE. An experimental design was prepared for both treatments in order to assess the effect of the treatment characteristics on the tensile load needed to break the bond between the ETFE and the acrylonitrile-butadiene-styrene polymer (ABS) formed with a cyanoacrylate adhesive (CAA) applied between them. The reason for the selection of this problem is that both polymers are frequently used in the biomedical industry for their properties, and they need to be joined firmly in biomedical devices, and the cyanoacrylate adhesive is the adhesive traditionally used for fluoropolymers, in this case the ETFE, and the same CAA has also shown good adhesion with ABS. However, the strength of the bond for the triplet ETFE-CAA-ABS has not been reported and the improvement of the strength of the bond with surface treatments is not found in scholarly journals for modern medical devices such as stents and snares. Both treatments were compared based on the aforementioned design of experiments. The case where ETFE receives no surface treatment serves as the reference. The results indicated that the three factors evaluated (initial drying of the material, temperature of the chemical bath, and immersion time), and their interactions have no significant effect over the tensile load at failure (tensile strength) of the adhesive bond being evaluated. For the air-ionization corona discharge treatment, two factors were evaluated: discharge exposition time and air pressure. The results obtained from this experimental design indicate that there is no significant difference between the levels of the factors evaluated. These results were unexpected as the ranges used were representative of the maximum ranges permissible in manufacturing

  2. Crystallization analysis fractionation of poly(ethylene-co-styrene) produced by metallocene catalysts

    KAUST Repository

    Kamal, Muhammad Shahzad


    Ethylene homo polymer and ethylene-styrene copolymers were synthesized using Cp2ZrCl2 (1)/methyl aluminoxane (MAO) and rac-silylene-bis (indenyl) zirconium dichloride (2)/MAO catalyst systems by varying styrene concentration and reaction conditions. Crystallization analysis fractionation (CRYSTAF), DSC, FTIR and 1H NMR spectroscopy were used for characterizing the synthesized polymers. Interestingly, styrene was able to increase the activity of 1/MAO and 2/MAO catalyst systems at low concentrations, but at higher concentrations the activity decreases. The 1/MAO system at low and high pressure was unable to incorporate styrene, and the final product was pure polyethylene. On the other hand, with 2/MAO polymerization of ethylene and styrene yielded copolymer containing both styrene and ethylene. Results obtained from CRYSTAF and DSC reveal that on using 1/MAO system at high pressure, the resulting polymer in the presence of styrene has similar crystallinity as the polymer produced without styrene. Using both 1/MAO at low pressure and 2/MAO leads to decrease in crystallinity with increase in styrene concentration, even though the former does not incorporate styrene. © 2013 Springer-Verlag Berlin Heidelberg.

  3. Manipulating the ABCs of self-assembly via low-χ block polymer design. (United States)

    Chang, Alice B; Bates, Christopher M; Lee, Byeongdu; Garland, Carol M; Jones, Simon C; Spencer, Russell K W; Matsen, Mark W; Grubbs, Robert H


    Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χAC [Formula: see text] 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAMP Transmission electron microscopy indicates that LAMP exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM3) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAMP is thermodynamically stable below a critical χAC, above which LAM3 emerges. Both experiments and theory expose close analogies to ABA' triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.

  4. Control of aggregation temperatures in mixed and blended cytocompatible thermoresponsive block co-polymer nanoparticles. (United States)

    Foralosso, Ruggero; Moir, Lee; Mastrotto, Francesca; Sasso, Luana; Tchoryk, Aleksandra; Selo, Amjad; Grabowska, Anna; Ashford, Marianne B; Aylott, Jonathan; Gellert, Paul R; Spain, Sebastian G; Alexander, Cameron


    A small library of thermoresponsive amphiphilic copolymers based on polylactide-block-poly((2-(2-methoxyethoxy)ethyl methacrylate)-co-(oligoethylene glycol methacrylate)) (PLA-b-P(DEGMA)-co-(OEGMA)), was synthesised by copper-mediated controlled radical polymerisation (CRP) with increasing ratios of OEGMA : DEGMA. These polymers were combined in two ways to form nanoparticles with controllable thermal transition temperatures as measured by particle aggregation. The first technique involved the blending of two (PLA-b-P(DEGMA)-co-(OEGMA)) polymers together prior to assembling nanoparticles (NPs). The second method involved mixing pre-formed nanoparticles of single (PLA-b-P(DEGMA)-co-(OEGMA)) polymers. The observed critical aggregation temperature Tt did not change in a linear relationship with the ratios of each copolymer either in the nanoparticles blended from different copolymers or in the mixtures of pre-formed nanoparticles. However, where co-polymer mixtures were based on (OEG)9MA ratios within 5-10 mole%, a linear relationship between (OEG)9MA composition in the blends and Tt was obtained. The data suggest that OEGMA-based copolymers are tunable over a wide temperature range given suitable co-monomer content in the linear polymers or nanoparticles. Moreover, the thermal transitions of the nanoparticles were reversible and repeatable, with the cloud point curves being essentially invariant across at least three heating and cooling cycles, and a selected nanoparticle formulation was found to be readily endocytosed in representative cancer cells and fibroblasts.

  5. Synthesis of ABA Tri-Block Co-Polymer Magnetopolymersomes via Electroporation for Potential Medical Application

    Directory of Open Access Journals (Sweden)

    Jennifer Bain


    Full Text Available The ABA tri-block copolymer poly(2-methyloxazoline–poly(dimethylsiloxane–poly(2-methyloxazoline (PMOXA–PDMS–PMOXA is known for its capacity to mimic a bilayer membrane in that it is able to form vesicular polymersome structures. For this reason, it is the subject of extensive research and enables the development of more robust, adaptable and biocompatible alternatives to natural liposomes for biomedical applications. However, the poor solubility of this polymer renders published methods for forming vesicles unreproducible, hindering research and development of these polymersomes. Here we present an adapted, simpler method for the production of PMOXA–PDMS–PMOXA polymersomes of a narrow polydispersity (45 ± 5.8 nm, via slow addition of aqueous solution to a new solvent/polymer mixture. We then magnetically functionalise these polymersomes to form magnetopolymersomes via in situ precipitation of iron-oxide magnetic nanoparticles (MNPs within the PMOXA–PDMS–PMOXA polymersome core and membrane. This is achieved using electroporation to open pores within the membrane and to activate the formation of MNPs. The thick PMOXA–PDMS–PMOXA membrane is well known to be relatively non-permeable when compared to more commonly used di-block polymer membranes due a distinct difference in both size and chemistry and therefore very difficult to penetrate using standard biological methods. This paper presents for the first time the application of electroporation to an ABA tri-block polymersome membrane (PMOXA–PDMS–PMOXA for intravesicular in situ precipitation of uniform MNPs (2.6 ± 0.5 nm. The electroporation process facilitates the transport of MNP reactants across the membrane yielding in situ precipitation of MNPs. Further to differences in length and chemistry, a tri-block polymersome membrane structure differs from a natural lipid or di-block polymer membrane and as such the application and effects of electroporation on this type of

  6. Synthesis and kinetics studies of poly(styrene-b-vinylmethylsiloxane) and its thin film ordering by thermal and solvent annealing (United States)

    Chatterjee, Sourav; Uddin, Md Fakar; Lwoya, Baraka; Albert, Julie N. L.

    Nano-structured thin film materials are important materials that find uses in templating and membrane applications. Block copolymers (BCP) have gained considerable attention for next-generation lithographic masks due to their self-assemble into morphologies with periodic sub 20 nm feature sizes with high regularity and reproducibility. A novel synthetic block copolymer of poly(styrene-b-vinylmethylsiloxane) (PS-b-PVMS) was synthesized. Like poly(styrene-b-dimethylsiloxane), this polymer has a high Flory Huggins interaction parameter between blocks to minimize feature size. Furthermore, incorporation of the vinyl side group provides an opportunity for post-polymerization chemical modification to manipulate the interaction parameter or impart functionality for various applications. Synthesis and kinetic studies of PS-b-PVMS as well as PS and PVMS homopolymers will be presented. All polymers are well characterized by proton NMR and GPC. As proof of concept, we show that block copolymers having different block fractions self-assemble into the expected nanostructures (lamellae, cylinders, spheres). Thin film studies also will be presented showing how the ordering of PS-b-PVMS is affected by different solvent and thermal annealing conditions.

  7. Development of bio-based polymers for use in asphalt. (United States)


    Asphalt binder is typically modified with poly type (styrene-butadiene-styrene or SBS) polymers to improve its rheological properties and performance grade. The elastic and principal component of SBS polymers is butadiene. For the last decade, butadi...

  8. Nanostructured Block Polymer Membranes as High Capacity Adsorbers for the Capture of Metal Ions from Water (United States)

    Boudouris, Bryan; Weidman, Jacob; Mulvenna, Ryan; Phillip, William

    The efficient removal of metal ions from aqueous streams is of significant import in applications ranging from industrial waste treatment to the purification of drinking water. An emerging paradigm associated with this separation is one that utilizes membrane adsorbers as a means by which to bind metal salt contaminants. Here, we demonstrate that the casting of an A-B-C triblock polymer using the self-assembly and non-solvent induced phase separation (SNIPS) methodology results in a nanoporous membrane geometry. The nature of the triblock polymer affords an extremely high density of binding sites within the membrane. As such, we demonstrate that the membranes with binding capacities equal to that of state-of-the-art packed bed columns. Moreover, because the affinity of the C moiety can be tuned, highly selective binding events can occur based solely on the chemistry of the block polymer and the metal ions in solution (i.e., in a manner that is independent of the size of the metal ions). Due to these combined facts, these membranes efficiently remove heavy metal (e.g., lead- and cadmium-based) salts from contaminated water streams with greater than 95% efficiency. Finally, we show that the membranes can be regenerated through a simple treatment in order to provide long-lasting adsorber systems as well. Thus, it is anticipated that these nanostructured triblock polymer membranes are a platform by which to obtain next-generation water purification processes.

  9. Amphiphilic block copolymers as efficiency boosters in microemulsions a SANS investigation of the role of polymers

    CERN Document Server

    Endo, H; Mihailescu, M; Monkenbusch, M; Gompper, G; Richter, D; Jakobs, B; Sottmann, T; Strey, R


    The effect of amphiphilic block copolymers on ternary microemulsions (water, oil and non-ionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic expansion of the one-phase region where water and oil can be solubilized by the mediation of surfactant molecules. Small-angle neutron-scattering experiments employing a high-precision two-dimensional contrast-variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane, where it modifies the membrane curvature elasticity. Furthermore, a new approach to determine the bending rigidity of an amphiphilic membrane is proposed, which is precise enough to measure the logarithmic scale dependence of the bending rigidity and its universal prefactor in bicontinuous microemulsions. (orig.)

  10. Amphiphilic block copolymers as efficiency boosters in microemulsions: a SANS investigation of the role of polymers

    Energy Technology Data Exchange (ETDEWEB)

    Endo, H.; Allgaier, J.; Mihailescu, M.; Monkenbusch, M.; Gompper, G.; Richter, D. [Institut fuer Festkoeperforschung, Forschungszentrum Juelich, 52425 Juelich (Germany); Jakobs, B.; Sottmann, T.; Strey, R. [Institut fuer Physikalische Chemie, Universitaet zu Koeln, Luxemburger Str. 116, 50939 Koeln (Germany)


    The effect of amphiphilic block copolymers on ternary microemulsions (water, oil and non-ionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic expansion of the one-phase region where water and oil can be solubilized by the mediation of surfactant molecules. Small-angle neutron-scattering experiments employing a high-precision two-dimensional contrast-variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane, where it modifies the membrane curvature elasticity. Furthermore, a new approach to determine the bending rigidity of an amphiphilic membrane is proposed, which is precise enough to measure the logarithmic scale dependence of the bending rigidity and its universal prefactor in bicontinuous microemulsions. (orig.)

  11. Preparation of Sufonated Poly (ethylene-co-tetrafluoroethylene-graft-styrene Based Polymer Electrolyte Membranes for Fuel Cell by using Gamma Irradiation Technique

    Directory of Open Access Journals (Sweden)

    A. Suliwarno


    Full Text Available Poly (ethylene-co-tetrafluoroethylene-graft-styrene-sulfonate was successfully prepared by irradiation grafting of a styrene monomer into ethylenetetrafluoro-ethylene (ETFE films and followed by sulfonation of the graft chains. Five film sheets of ETFE which having a size of 3 cm  8 cm, thickness of 25 µm were packed in vacuum using a Y type tube filled with argon gas. The samples were irradiated using γ-rays with a dose of 15 kGy at 15 kGy/h. The iradiated samples were grafted by using styrene monomer at 60o C for 1, 3, 5, 7 and 9 h, respectively. The grafted samples (ETFE-g-St were washed with xylene to remove homopolymer of polystyrene, and then its degree of grafting (DG was determined. Sulfonation was carried out by using 0.2 M chlorosulfonic acid in dichloroethane solution at a water bath of 60oC for 6 h. Sulfonated samples (ETFE-g-St-SO3H were washed with water to neutralize its acidity, and dried in a vacuum drier at 40oC for 15 h. The dried sample was weighed as sulfonated sample in order to determine the degree of sulfonation (%DS. Membrane properties of EFTE-g-St-SO3H sample such as ion exchange capacity (IEC, proton conductivity in cross direction (σ1, and in-plane direction (σ11 were determined by using a HIOKI-3522 LCR HI tester. Durability test of samples were conducted in hot water and 3% H2O2 respectively.. The proton conductivity measurement and durability of the membrane were compared to Nafion 112® as standard. The experimental results showed that the degree of grafting was increased with time of reaction for copolymerization, while %DS gave excellent results with an average of 92.7%. The IEC value was more affected by the %DG as compared to that of %DS effect. The average of σl value of the sample was 0.055 S/cm, compared to σl of Nafion112® that was 0.066 S/cm. The average of ll of the sample was 0.18 S/cm, while the ll of Nafion 112® was = 0.36 S/cm. The sample of SA004 with 53.49% DG was more stable than

  12. Hybrid Block Copolymers Constituted by Peptides and Synthetic Polymers: An Overview of Synthetic Approaches, Supramolecular Behavior and Potential Applications

    Directory of Open Access Journals (Sweden)

    Jordi Puiggalí


    Full Text Available Hybrid block copolymers based on peptides and synthetic polymers, displaying different types of topologies, offer new possibilities to integrate the properties and functions of biomacromolecules and synthetic polymers in a single hybrid material. This review provides a current status report of the field concerning peptide-synthetic polymer hybrids. The first section is focused on the different synthetic approaches that have been used within the last three years for the preparation of peptide-polymer hybrids having different topologies. In the last two sections, the attractive properties, displayed in solution or in the solid state, together with the potential applications of this type of macromolecules or supramolecular systems are highlighted.

  13. Fracture behavior of block copolymer and graphene nanoplatelet modified epoxy and fiber reinforced/epoxy polymer composites (United States)

    Kamar, Nicholas T.

    Glass and carbon fiber reinforced/epoxy polymer composites (GFRPs and CFRPs) have high strength-to-weight and stiffness-to-weight ratios. Thus, GFRPs and CFRPs are used to lightweight aircraft, marine and ground vehicles to reduce transportation energy utilization and cost. However, GFRP and CFRP matrices have a low resistance to crack initiation and propagation; i.e. they have low fracture toughness. Current methods to increase fracture toughness of epoxy and corresponding GFRP and CFRPs often reduce composite mechanical and thermomechanical properties. With the advent of nanotechnology, new methods to improve the fracture toughness and impact properties of composites are now available. The goal of this research is to identify the fracture behavior and toughening mechanisms of nanoparticle modified epoxy, GFRPs and CFRPs utilizing the triblock copolymer poly(styrene)-block-poly(butadiene)-block-poly(methylmethacrylate) (SBM) and graphene nanoplatelets (GnPs) as toughening agents. The triblock copolymer SBM was used to toughen the diglycidyl ether of bisphenol-A (DGEBA) resin cured with m-phenylenediamine (mPDA) and corresponding AS4-12k CFRPs. SBM self assembled in epoxy to form nanostructured domains leading to larger increases in fracture toughness, KQ (MPa*m 1/2) than the traditional, phase separating carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. Additionally, SBM increased the mode-I fracture toughness, GIc (J/m2) of CFRPs without corresponding reductions in composite three-point flexural properties and glass transition temperature (Tg). Fractography of SBM modified epoxy and CFRPs via scanning electron microscopy (SEM) showed that sub 100 nm spherical micelles cavitated to induce void growth and matrix shear yielding toughening mechanisms. Furthermore, SBM did not suppress epoxy Tg, while CTBN decreased Tg with both increasing concentration and acrylonitrile content. Graphene nanoplatelets (GnPs) consist of a few layers of graphene sheets, which

  14. Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method. (United States)

    Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping


    The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis and characterization of novel polymer-drug conjugates based on the poly(styrene-alt-maleic anhydride) as a potential method for drug release. (United States)

    Khazaei, Ardeshir; Saednia, Shahnaz; Saien, Javad; Borazjani, Maryam Kiani; Rahmati, Sadegh; Hashempour-Zaviye, Ali; Abbasi, Fatemeh


    Six well known drugs, captopril, metformin-HCl, metroniazole, nortriptyline-HCl, fluoxetine-HCl and betahistin-HCl, were grafted to poly(styrene-alt-maleic anhydride) (PSMA). Grafting was attained by combining of anhydride groups in the PSMA with therapeutic agents containing NH, OH or SH groups. The covalently grafted drugs were identified by infrared, (1)H NMR and UV-Vis spectroscopy. The drug release data at different times fits well to the Korsmeyer-Peppas equation. The analysis of the exponent n of this model revealed a dominant Fickian diffusion mechanism under the in vitro conditions. Furthermore, mean dissolution time values (45.9 to 86.7 h) indicate a high resistance against drugs transport, the highest being obtained for betahistin-HCL.

  16. New highly fluorinated styrene-based materials with low surface energy prepared by ATRP

    DEFF Research Database (Denmark)

    Borkar, Sachin; Jankova Atanasova, Katja; Siesler, Heinz W


    2,3,5,6-Tetrafluoro-4-(2,2,3,3,3-pentafluoropropoxy)styrene (TF(F-5)S) and 2,3,5,6-tetrafluoro-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctaoxy)styrene (TF(F,5)S) are prepared by nucleophilic substitution of 2,3,4,5,6-pentafluorostyrene. The neat monomers are subjected to atom transfer...... radical polymerization (ATRP) at 110 degreesC to high conversions in relatively short times, 10-120 min; TF(F-5)S is additionally polymerized at 70 and 90 degreesC. Block copolymers with styrene are prepared by the macroinitiator approach. All polymers, in the number-average molecular weight range from...... than 10 mol %. The fluorinated side chains of P(TF(F-5)S) and P(TF(F-15)S) enrich the surface of thin films, which results in an advancing water contact angle of 117degrees and 122degrees, respectively. Both XPS analyses and contact angle measurements strongly imply that the fluorinated parts...

  17. Enhancing relative permittivity by incorporating PDMS-PEG multi block copolymers in binary polymer blends

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts a possibil......Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts...... a possibility for substantial improvement of properties such as high permittivity, stretchability and non-conductivity – if carefully designed. The objective is to synthesize PDMS-PEG multiblock copolymer assembling into discontinuous morphologies in PEG based on variation of volume fractions of PDMS....... The utilized synthesis of PDMS-PEG multiblock copolymer is based on hydrosilylation reaction, which is amended from Klasner et al.1 and Jukarainen etal.2 Variation in the ratio between the two constituents introduces distinctive properties in terms of dielectric permittivity and rheological behaviour. PDMS...

  18. Salt Distribution, Domain Spacing, and Interfacial Characteristics in Lithium Ion-Doped Block Polymer Electrolyte Films (United States)

    Gartner, Thomas; Shelton, Cameron; Morris, Melody; Jayaraman, Arthi; Epps, Thomas, III

    Block polymer (BP) electrolytes have significant potential for use as battery membranes; however, to enable the design of efficient and reliable battery materials, open questions must be answered about the effects of lithium ion dopants on BP microstructure (including domain spacing and mixing near the interface) and the distribution of lithium ions in the BP domains. In this work, X-ray and neutron reflectometry (XRR and NR, respectively) revealed the morphological changes introduced by doping lamellar polystyrene- b-poly(oligo(oxyethylene methacrylate)) (PS-POEM) block polymer films with various lithium salts, as well as the lithium ion distribution in the ion-conducting POEM domain. XRR indicated swelling of both the POEM and PS domains with increasing salt content, with a corresponding decrease in the interfacial width as the salt increased the segregation strength of the BP. However, at very high salt concentrations ([EO]:[Li] = 6:1), roughening of the film caused a slight increase in the interfacial width. NR showed similar trends in domain spacing with salt content, and fits to the NR allow for determination of the lithium salt distribution across the POEM domains. These results help identify the implications of doping lithium salts into BP battery membranes and inform the design of BP electrolyte materials with controlled structure and properties.

  19. Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation. (United States)

    Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H


    Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene-b-ethylene oxide) or pure poly(butadiene-b-ethylene oxide-d4) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

  20. The nature of protein interactions governing globular protein-polymer block copolymer self-assembly. (United States)

    Lam, Christopher N; Kim, Minkyu; Thomas, Carla S; Chang, Dongsook; Sanoja, Gabriel E; Okwara, Chimdimma U; Olsen, Bradley D


    The effects of protein surface potential on the self-assembly of protein-polymer block copolymers are investigated in globular proteins with controlled shape through two approaches: comparison of self-assembly of mCherry-poly(N-isopropylacrylamide) (PNIPAM) bioconjugates with structurally homologous enhanced green fluorescent protein (EGFP)-PNIPAM bioconjugates, and mutants of mCherry with altered electrostatic patchiness. Despite large changes in amino acid sequence, the temperature-concentration phase diagrams of EGFP-PNIPAM and mCherry-PNIPAM conjugates have similar phase transition concentrations. Both materials form identical phases at two different coil fractions below the PNIPAM thermal transition temperature and in the bulk. However, at temperatures above the thermoresponsive transition, mCherry conjugates form hexagonal phases at high concentrations while EGFP conjugates form a disordered micellar phase. At lower concentration, mCherry shows a two-phase region while EGFP forms homogeneous disordered micellar structures, reflecting the effect of changes in micellar stability. Conjugates of four mCherry variants with changes to their electrostatic surface patchiness also showed minimal change in phase behavior, suggesting that surface patchiness has only a small effect on the self-assembly process. Measurements of protein/polymer miscibility, second virial coefficients, and zeta potential show that these coarse-grained interactions are similar between mCherry and EGFP, indicating that coarse-grained interactions largely capture the relevant physics for soluble, monomeric globular protein-polymer conjugate self-assembly.

  1. Multi-modal switching in responsive DNA block co-polymer conjugates. (United States)

    Yaşayan, Gökçen; Magnusson, Johannes P; Sicilia, Giovanna; Spain, Sebastian G; Allen, Stephanie; Davies, Martyn C; Alexander, Cameron


    New classes of information-rich DNA block co-polymer conjugates were synthesised, encoded with thermoresponsive and biocompatible poly(tri(ethylene glycol)ethyl ether methacrylate) (pTriEGMA) chains and oligomeric nucleic acids connected by either bioreducible or non-reducible links. The pTriEGMA chains were grown from initiator-functionalised hybridised DNA, designed to assemble with toehold overhangs. Functional information in the conjugates was explored via dynamic light scattering (DLS) and atomic force microscopy (AFM), in order to evaluate (i) reversible self-assembly into supramolecular structures across the pTriEGMA phase transition temperature; (ii) conformational change via addition of competing DNA sequences across the toeholds, and (iii) reductive cleavage of polymer-DNA links. The results showed that discrete nanoscale conjugates could reversibly associate through pTriEGMA phase behaviour and that size and association behaviour in one class of conjugate could be switched by addition of a competing DNA sequence and by reduction to break the polymer-DNA links. Preliminary experiments with the DNA-conjugates as delivery systems for doxorubicin to a cancer cell line indicated good tolerability of the conjugates alone and cytotoxic efficacy when loaded with the drug.

  2. Gloss and Stain Resistance of Ceramic-Polymer CAD/CAM Restorative Blocks. (United States)

    Lawson, Nathaniel C; Burgess, John O


    To evaluate the gloss and stain resistance of several new ceramic-polymer CAD/CAM blocks Specimens (4 mm) were sectioned from: Enamic (polymer-infused ceramic), LAVA Ultimate (nano-ceramic reinforced polymer), e.max (lithium disilicate), Paradigm C (porcelain), and Paradigm MZ100 (composite). Specimens were wet polished on a polishing wheel to either 320 grit silicon paper (un-polished, N = 8) or 2000 grit silicon carbide papers followed by a 0.05 μm alumina slurry (polished, N = 8). Initial gloss and color (L*a*b*) values were measured. Specimens were stored in a staining solution at 37°C in darkness for 12 days (simulating 1 year). After storage, L*a*b* values re-measured. Change in color was reported as ΔE00 based on the CIEDE2000 formula. Gloss and ΔE00 were analyzed by two-way analysis of variance (ANOVA) (alpha = .05). Separate one-way ANOVA and Tukey post-hoc analyses were performed for both polish conditions and all materials. Two-way ANOVA showed that factors material, polish and their interaction were significant for both gloss and ΔE00 (p < .01). Post-hoc analysis reveals that polished specimens had significantly less color change than un-polished specimens for Paradigm C and LAVA Ultimate. E.max had significantly higher gloss and less color change than all other materials. The composition and polish of CAD/CAM materials affects gloss and stain resistance. Ceramic-polymer hybrid materials can achieve the high gloss required for esthetic restorations. These materials should be polished in order to minimize staining. If polished, all of the tested materials exhibited clinically acceptable color changes at 1 year of simulated staining. (J Esthet Restor Dent 28:S40-S45, 2016). © 2015 Wiley Periodicals, Inc.

  3. Solubilization of Phenol Derivatives in Polymer Micelles Formed by Cationic Block Copolymer

    Directory of Open Access Journals (Sweden)

    Irma Fuentes


    Full Text Available The aggregation of cationic block copolymers formed by polystyrene (PS and poly(ethyl-4-vinylpyridine (PS-b-PE4VP was studied in aqueous solution. Diblock copolymers of PS and poly(4-vinylpyridine were synthesized by sequential anionic polymerization using BuLi as initiator. Subsequently, the 4-vinylpyridine units were quaternized with ethyl bromide to obtain cationic PS-b-PE4VP block copolymers with different quaternization degree. The self-aggregation of cationic block copolymers was studied by fluorescence probing, whereas the morphology and size of polymer micelles were determined by transmission electronic microscopy. Results indicate that spherical micelles with sizes lower than 100 nm were formed, whereas their micropolarity decreases with increasing quaternization degree. The partition of phenols between the micellar and aqueous phase was studied by using the pseudo-phase model, and the results show that the partition coefficients increase with increasing length of the side alkyl chain and are larger for star micelles. These results are discussed in terms of three-region model.

  4. Nanoporous Thermosets with Percolating Pores from Block Polymers Chemically Fixed above the Order–Disorder Transition

    Energy Technology Data Exchange (ETDEWEB)

    Vidil, Thomas; Hampu, Nicholas; Hillmyer, Marc A. (UMM)


    A lamellar diblock polymer combining a cross-linkable segment with a chemically etchable segment was cross-linked above its order–disorder temperature (TODT) to kinetically trap the morphology associated with the fluctuating disordered state. After removal of the etchable block, evaluation of the resulting porous thermoset allows for an unprecedented experimental characterization of the trapped disordered phase. Through a combination of small-angle X-ray scattering, nitrogen sorption, scanning electron microscopy, and electron tomography experiments we demonstrate that the nanoporous structure exhibits a narrow pore size distribution and a high surface to volume ratio and is bicontinuous over a large sample area. Together with the processability of the polymeric starting material, the proposed system combines attractive attributes for many advanced applications. In particular, it was used to design new composite membranes for the ultrafiltration of water.

  5. Lipid-induced degradation in biocompatible poly(Styrene-Isobutylene-Styrene) (SIBS) thermoplastic elastomer. (United States)

    Fittipaldi, Mauro; Grace, Landon R


    The thermoplastic elastomer Poly(Styrene-block-Isobutylene-block-Styrene) (SIBS) is highly biocompatible, which has led to its use in several commercially-available implants. However, lipid-induced degradation has been previously identified as a primary cause of failure in long-term SIBS implants subject to mechanical loading. Thus, understanding the mechanisms and extent of lipid-induced damage and the role of styrene-isobutylene ratio and molecular weight is critical to improving longevity of SIBS-based implants in order to fully exploit the biocompatibility advantages. Samples of four different SIBS formulations were fabricated via compression molding, immersed to lipid saturation contents from 5 to 80% by weight, and tested in uniaxial tension, stress relaxation, and dynamic creep modes. Degradation mechanisms were investigated via infrared spectroscopy, chromatography, and microscopy. No evidence of lipid-induced chemical interactions or chain scissoring was observed. However, a decrease in tensile strength, loss of dynamic creep performance and faster relaxation with increasing lipid content is attributed to strong internal straining. The magnitude of these losses is inversely proportional to both molecular weight and styrene content, suggesting that selection of these variables during the design phase should be based not only on the mechanical requirements of the application, but the expected degree of lipid exposure. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Kazuhiro Nakabayashi


    Full Text Available This review summarizes recent advances in the design and synthesis of novel complex polymers with carbazole moieties using controlled radical polymerization techniques. We focus on the polymeric architectures of block copolymers, star polymers, including star block copolymers and miktoarm star copolymers, comb-shaped copolymers, and hybrids. Controlled radical polymerization of N-vinylcarbazole (NVC and styrene and (methacrylate derivatives having carbazole moieties is well advanced, leading to the well-controlled synthesis of complex macromolecules. Characteristic optoelectronic properties, assembled structures, and three-dimensional architectures are briefly introduced.

  7. Direct methanol fuel cell based on poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO 2/PSSA) composite polymer membrane (United States)

    Yang, Chun-Chen; Chien, Wen-Chen; Li, Yingjeng James

    The high performance poly(vinyl alcohol)/titanium oxide nanotubes/poly(styrene sulfonic acid) (PVA/nt-TiO 2/PSSA) proton-conducting composite membrane is prepared by a solution casting method. The characteristic properties of these blend composite membranes are investigated by thermal gravimetric analysis (TGA), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), micro-Raman spectroscopy, dynamic mechanical analysis (DMA), methanol permeability measurement and AC impedance method. It is found that the peak power densities of the DMFC with 1, 2, and 4 M CH 3OH fuels are 12.85, 23.72, and 10.99 mW cm -2, respectively, at room temperature and ambient air. Especially, among three methanol concentrations, the 2 M methanol shows the highest peak power density among three methanol concentrations. The results indicate that the air-breathing direct methanol fuel cell comprised of a novel PVA/nt-TiO 2/PSSA composite polymer membrane has excellent electrochemical performance and stands out as a viable candidate for applications in DMFC.

  8. Ion-exclusion chromatographic behavior of aliphatic carboxylic acids and benzenecarboxylic acids on a sulfonated styrene--divinylbenzene co-polymer resin column with sulfuric acid containing various alcohols as eluent. (United States)

    Ohta, Kazutoku; Towata, Atsuya; Ohashi, Masayoshi


    The addition of C1-C7 alcohols (methanol, ethanol, propanol, butanol, heptanol, hexanol and heptanol) to dilute sulfuric acid as eluent in ion-exclusion chromatography using a highly sulfonated styrene-divinylbenzene co-polymer resin (TSKgel SCX) in the H+ form as the stationary phase was carried out for the simultaneous separations of both (a) C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, isobutyric, butyric, isovaleric, valeric, 2-methylvaleric, isocaproic, caproic, 2,2-dimethyl-n-valeric, 2-methylhexanoic, 5-methylhexanoic and heptanoic acids) and (b) benzenecarboxylic acids (pyromellitic, hemimellitic, trimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic and salicylic acids and phenol). Heptanol was the most effective modifier in ion-exclusion chromatography for the improvement of peak shapes and a reduction in retention volumes for higher aliphatic carboxylic acids and benzenecarboxylic acids. Excellent simultaneous separation and relatively highly sensitive conductimetric detection for these C1-C7 aliphatic carboxylic acids were achieved on the TSKgel SCX column (150 x 6 mm I.D.) in 30 min using 0.5 mM sulfuric acid containing 0.025% heptanol as eluent. Excellent simultaneous separation and highly sensitive UV detection at 200 nm for these benzenecarboxylic acids were also achieved on the TSKgel SCX column in 30 min using 5 mM sulfuric acid containing 0.075% heptanol as eluent.

  9. Studies on polymer-coated zinc oxide nanoparticles: UV-blocking efficacy and in vivo toxicity. (United States)

    Girigoswami, Koyeli; Viswanathan, Meenakshi; Murugesan, Ramachandran; Girigoswami, Agnishwar


    Zinc oxide (ZnO) is explicitly used in sunscreens and cosmetic products; however, its effect in vivo is toxic in some cases. The UV blocking efficacy of ZnO nanoparticles is lost due to photocatalysis. To isolate a lower toxic species of sunblockers, ZnO nanoparticles were synthesized and coated with chitosan - a natural polymer (ZnO-CTS) and polyethylene glycol (PEG) - a synthetic polymer (ZnO-PEG). Coating with CTS and PEG circumvented the photocatalytic activity, increased the stability and improved the UV absorption efficacy. The effect of ZnO, ZnO-CTS and ZnO-PEG nanoparticles in vivo on zebrafish embryo revealed lower deposition of ZnO-CTS and ZnO-PEG nanoparticles atop the eggs compared to ZnO. The survival of zebrafish embryos was always found to be higher in case of ZnO-CTS with respect to ZnO-treated ones. PEG coating exhibited better UV attenuation, but, in vivo it induced delayed hatching. Thus, one of the reasons for better survival could be attributed to lower aggregation of ZnO-CTS nanoparticles atop eggs thereby facilitating the breathing of embryos. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries. (United States)

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


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

  11. Role of corona block in molecular exchange in block copolymer micelles (United States)

    Wang, En; Lu, Jie; Lodge, Timothy; Bates, Frank

    Self-assembled block polymer micelles are used in a variety of applications including drug delivery and viscosity modification as additives to motor lubricants. Previous work with dilute solutions of poly(styrene-b-ethylene-alt-propylene) (PS-PEP) diblock copolymer micelle has resulted in a theoretical model that accounts for the dramatic influence of the PS core block length and dispersity on chain exchange kinetics in squalane, a selective neutral solvent for PEP. This model, which accounts for the significant effect of core block length and its polydispersity on chain exchange kinetics, does not address the role of the corona block length. This presentation will describe the consequences of varying the size of the PEP corona block at constant core molecular weight on the rate of chain exchange based on time-resolved small-angle neutron scattering (TR-SANS) measurements. These results have informed an improved model that explicitly includes a corona term.

  12. New dual-phase polymer electrolytes prepared from NBR/SBR lattices. [polyacryloNitrile-Butadiene Rubber/poly(Styrene-Butadiene) copolymer Rubber

    Energy Technology Data Exchange (ETDEWEB)

    Matsumoto, Morihiko; Ichino, Toshihiro; Rutt, J.S.; Nishi, Shiro (Nippon Telegraph and Telephone Corp., Tokyo (Japan). NTT Interdisciplinary Research Lab.)


    A new type of Li[sup +] ion conducting polymer electrolytes consisting of two phases, one of which is a highly polar region (impregnated with lithium salt solution), forming ion-conductive channels, while the other is a nonpolar region, forming supporting polymer matrices have been prepared from NBR/SBR lattices. TEM measurement and EDX analysis show evidence that dual-phase structure is constructed in the electrolyte. Ionic conductivity of the electrolyte increases with increase of lithium salt solution content. Maximum ionic conductivity of 2.2 [times] 10[sup [minus]3] S/cm is obtained at the lithium salt solution content of 60.5% (w/w). The electrolyte retains rubber-like film with good mechanical strength despite the presence of the solution.

  13. Prediction of drug solubility in amphiphilic di-block copolymer micelles: the role of polymer-drug compatibility. (United States)

    Latere Dwan'Isa, J P; Rouxhet, L; Préat, V; Brewster, M E; Ariën, A


    The goal of the current study was to assess the value of predictive computational approaches for estimating drug solubility in hydrated micelles formed from di-block copolymers of polyethylene glycol (PEG) and random copolyesters of epsilon-caprolactone (CL) and trimethylene carbonate (TMC) using drug-polymer compatibility as assessed through the Flory-Huggins interaction parameter (chi). In order to accomplish this, the compatibility of several well-known model drugs (associated with the four biopharmaceutics classification system (BCS) classes) was assessed with both segments of the amphiphilic di-block copolymer PEG-b-P(CL-co-TMC). Compatibilities were estimated based on the Hansen modification of the Hildebrand approach using Molecular Modeling Pro software. Experimental solubilities for model drugs were determined using a shake-flask technique at various polymer concentrations. The solubilities of 8 compounds in 10% w/v micelle solutions were in relatively good agreement with the predicted drug-polymer compatibility. In addition, the approach allows for the selection of a suitable di-block copolymer for optimal solubilization of a specific drug. Furosemide was assessed as a model with results suggesting that it can be best entrapped in a di-block copolyester containing a relatively high CL content. The data suggests that prediction of drug solubilization of block copolymer-based micelles may be facilitated by assessing the compatibility of the drug for the component polymeric domains.

  14. The influence of mechanical properties in the electrical breakdown in poly-styrene-ethylene-butadiene-styrene thermoplastic elastomer (United States)

    Kollosche, Matthias; Melzer, Michael; Becker, Andre; Stoyanov, Hristian; McCarthy, Denis N.; Ragusch, Hülya; Kofod, Guggi


    Dielectric elastomer actuators (DEA) are a class of eletro-active polymers with promising properties for a number of applications, however, such actuators are prone to failure. One of the leading failure mechanisms is the electrical breakdown. It is already well-known that the electro-mechanical actuation properties of DEA are strongly influenced by the mechanical properties of the elastomer and compliant electrodes. It was recently suggested that also the electrical breakdown in such soft materials is influenced by the mechanical properties of the elastomer. Here, we present stress-strain measurements obtained on two tri-block thermoplastic elastomers (SEBS 500040 and SEBS 500120, poly-styrene-ethylene-butadiene-styrene), with resulting large differences in mechanical properties, and compare them to measurements on the commonly used VHB 4910. Materials were prepared by either direct heat-pressing of the raw material, or by dissolving in toluene, centrifuging and drop-casting. Experiments showed that materials prepared with identical processing steps showed a difference in stiffness of about 20%, where centrifuged and drop-casted films were seen to be softer than heat-pressed films. Electric breakdown measurements showed that for identically processed materials, the stiffness seemed to be a strong indicator of the electrical breakdown strength. It was therefore found that processing leads to differences in both stiffness and electrical breakdown strength. However, unexpectedly, the softer drop-cast films had a much higher breakdown strength than the heatpressed films. We attribute this effect to impurities still present in the heat-pressed films, since these were not purified by centrifuging.

  15. Synthesis of segmented (pb(ps-block-pb)(n)) and (pb(san-block- pb)(n)) block-copolymers via polymeric thermal iniferters

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G


    A technique is described for the synthesis of segmented poly(butadiene-block-styrene) block copolymers and segmented poly(butadiene-block-(styrene-co-acrylonitrile)) block copolymers through polybutadiene-based thermal iniferters. Dihydroxy- and dicarboxy-terminated polybutadienes were transformed

  16. Cocontinuous polymer blends: The role of block copolymer in blend morphology evolution (United States)

    Bell, Joel Richard

    Cocontinuous morphologies are distinguished by the mutual interpenetration of two polymer phases and allow for enhanced mechanical properties, static charge dissipation, and barrier properties. Cocontinuous morphologies form over a range of compositions, depending largely on mixing history and the relative polymer viscosities, elasticities, and interfacial tension. Because cocontinuous morphologies are thermodynamically unstable, they will coarsen when held above their glass or melt transition temperature. Since the unique properties of these blends depend directly on the continuous nature of the microstructure and its phase size, stabilization of the cocontinuous morphology is extremely important. To address this challenge, compatibilizers, e.g. block copolymers (bcp), are often added to hinder phase coarsening in blends of immiscible polymers and can improve bonding at interfaces. The effects of bcp on the cocontinuous morphology of polystyrene (PS)/polyethylene (PE) and PS/poly(methyl methacrylate) (PMMA) blends were studied using scanning electron microscopy (SEM) with image analysis, 3D imaging, mercury porosimetry, solvent extraction, and rheology. It was shown that diblock copolymers were able to suppress coarsening during annealing in cocontinuous PS/PE and PS/PMMA blends. Bcp effectiveness was dependent on molecular weight, concentration, and architecture. Self consistent mean field theory and bending elasticity theory were used to estimate the proper bcp architecture for maximum reduction in interfacial tension; experimental results agreed well with the theory. In addition to slowing coarsening, bcp was shown to widen the range of cocontinuity for both the PS/PE and PS/PMMA systems. To aid determination of the range of cocontinuity, a new technique for analyzing SEM micrographs was developed. The new technique classifies blend morphology according to the normalized fraction of drops present in the 2D microstructure. It was found that a blend becomes

  17. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles. (United States)

    Nakamura, Issei


    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  18. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    Energy Technology Data Exchange (ETDEWEB)

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.


    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  19. Reversal of β-oxidative pathways for the microbial production of chemicals and polymer building blocks. (United States)

    Kallscheuer, Nicolai; Polen, Tino; Bott, Michael; Marienhagen, Jan


    β-Oxidation is the ubiquitous metabolic strategy to break down fatty acids. In the course of this four-step process, two carbon atoms are liberated per cycle from the fatty acid chain in the form of acetyl-CoA. However, typical β-oxidative strategies are not restricted to monocarboxylic (fatty) acid degradation only, but can also be involved in the utilization of aromatic compounds, amino acids and dicarboxylic acids. Each enzymatic step of a typical β-oxidation cycle is reversible, offering the possibility to also take advantage of reversed metabolic pathways for applied purposes. In such cases, 3-oxoacyl-CoA thiolases, which catalyze the final chain-shortening step in the catabolic direction, mediate the condensation of an acyl-CoA starter molecule with acetyl-CoA in the anabolic direction. Subsequently, the carbonyl-group at C3 is stepwise reduced and dehydrated yielding a chain-elongated product. In the last years, several β-oxidation pathways have been studied in detail and reversal of these pathways already proved to be a promising strategy for the production of chemicals and polymer building blocks in several industrially relevant microorganisms. This review covers recent advancements in this field and discusses constraints and bottlenecks of this metabolic strategy in comparison to alternative production pathways. Copyright © 2017 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  20. Structure of thiophene-based regioregular polymers and block copolymers and its influence on luminescence spectra

    NARCIS (Netherlands)

    van Hutten, Paul; Gill, R.E; Herrema, J.K; Hadziioannou, G


    Two approaches toward control of the luminescence wavelength of polythiophenes have been explored: (i) block copolymers in which oligothiophene blocks alternate with oligosilanylene blocks and (ii) regioregular polythiophenes in which oligothiophene sequences are delimited by n-octyl substituents

  1. The effect of different component ratios in block polymers and processing conditions on electrodeposition efficiency onto titanium

    Energy Technology Data Exchange (ETDEWEB)

    Fukuhara, Yusuke; Kyuzo, Megumi [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Tsutsumi, Yusuke [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-surugadai, Chiyoda-ku, Tokyo 101-0062 (Japan); Nagai, Akiko [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-surugadai, Chiyoda-ku, Tokyo 101-0062 (Japan); Chen, Peng [Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-surugadai, Chiyoda-ku, Tokyo 101-0062 (Japan); Hanawa, Takao, E-mail: [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-surugadai, Chiyoda-ku, Tokyo 101-0062 (Japan)


    Graphical abstract: - Highlights: • MPC polymers with an ability of electrodeposition were synthesized. • MPC polymers were immobilized on titanium substrates by electrodeposition. • Immobilization by electrodeposition of MPC polymer decreased water contact angle and protein adsorption. • Length of MPC unit and electrodeposition time did not influence water contact angle and protein adsorption. - Abstract: 2-Methacryloyloxyethyl phosphorylcholine (MPC) polymers for electrodeposition to titanium surfaces were synthesized. The polymers were block-type copolymers composed of a poly(MPC) segment and a poly(2-aminoethylmethacrylate (AEMA)) segment, which could electronically adsorb to a titanium oxide film on the titanium surface. The polymer was synthesized as expected by nuclear magnetic resonance and gel permeation chromatography. In a 0.26 mmol L{sup −1} PMbA solution adjusted to pH 11, −3.0 V (vs. an Ag/AgCl electrode) was applied to a titanium substrate for 300 s. We evaluated the effects of the molecular structure of poly(MPC-block-AEMA) (PMbA) with a different polymerization degree of MPC unit, whereas the polymerization degree of the AEMA units was fixed. The 15-min electrodeposition of PMbA100 was the most efficient condition in this study. On the other hand, the results of the water contact angle and the amount of adsorbed protein did not change, even when altering the MPC unit number and electrodeposition time. This indicates that the immobilization by electrodeposition of PMbA is important for the inhibition of protein adsorption, while the polymerization degree of the MPC unit and the electrodeposition time do not influence them. This study will enhance the understanding of effective polymer structures for electrodeposition and electrodeposition conditions.

  2. The effect of different component ratios in block polymers and processing conditions on electrodeposition efficiency onto titanium (United States)

    Fukuhara, Yusuke; Kyuzo, Megumi; Tsutsumi, Yusuke; Nagai, Akiko; Chen, Peng; Hanawa, Takao


    2-Methacryloyloxyethyl phosphorylcholine (MPC) polymers for electrodeposition to titanium surfaces were synthesized. The polymers were block-type copolymers composed of a poly(MPC) segment and a poly(2-aminoethylmethacrylate (AEMA)) segment, which could electronically adsorb to a titanium oxide film on the titanium surface. The polymer was synthesized as expected by nuclear magnetic resonance and gel permeation chromatography. In a 0.26 mmol L-1 PMbA solution adjusted to pH 11, -3.0 V (vs. an Ag/AgCl electrode) was applied to a titanium substrate for 300 s. We evaluated the effects of the molecular structure of poly(MPC-block-AEMA) (PMbA) with a different polymerization degree of MPC unit, whereas the polymerization degree of the AEMA units was fixed. The 15-min electrodeposition of PMbA100 was the most efficient condition in this study. On the other hand, the results of the water contact angle and the amount of adsorbed protein did not change, even when altering the MPC unit number and electrodeposition time. This indicates that the immobilization by electrodeposition of PMbA is important for the inhibition of protein adsorption, while the polymerization degree of the MPC unit and the electrodeposition time do not influence them. This study will enhance the understanding of effective polymer structures for electrodeposition and electrodeposition conditions.

  3. The Effect of Block Copolymer Adsorption on Thin Film Dewetting Kinetics (United States)

    Costa, A. C.; Oslanec, R.; Composto, R. J.; Vlcek, P.


    Using optical microscopy, the dewetting kinetics of thin polystyrene films from a solid substrate is studied as a function of block copolymer adsorption at the polymer/solid interface. The block copolymer is poly(styrene-block-methylmethacrylate) (PS-b-PMMA) which contains short MMA and long S blocks. The MMA block adsorbs to the silicon oxide surface, whereas the S block extends into the matrix polymer. The matrix is formed by a polystyrene (PS) homopolymer. The dewetting kinetics of PS films, with and without PS-b-PMMA, is investigated by measuring the hole diameter as a function of time, at constant temperature for various molecular weights and concentrations of PS-b-PMMA in the film. We find that the presence of adsorbing block copolymer at the polymer/solid interface can significantly retards the dewetting dynamics of thin polymer films by increasing the adhesion between the polymer film and the substrate. These macroscopic results are correlated with the molecular aspects of block copolymer adsorption, such as the volume fraction profile and the coverage of the adsorbed layer.

  4. Processing Cyclic Peptide-polymer Conjugates in Block Copolymer Thin Films for Sub-nm Porous Membranes (United States)

    Zhang, Chen; Xu, Ting


    Porous thin films containing subnanometer channels oriented normal to the surface exhibit unique transport and separation properties and can serve as selective membranes for separation. Inspired by natural protein channels, we have developed an approach using cyclic peptide nanotubes (CPNs) embedded in polymeric matrix to mimic the transport of natural channels. The co-assembly of polymer-covered CPNs in a block copolymer (BCP) thin film requires the synchronization of two self-assembly processes, namely the microphase separation of BCP and the nanotube growth of CP-polymer conjugates. We systematically investigated the co-assembly of isolated CP-poly(ethylene glycol) (CP-PEG) conjugates and polystyrene-b-poly (methyl methacrylate) (PS-b-PMMA) in thin films as a function of CP-PEG loading (fCP-PEG) and solvent-polymer interactions. We find that there is a strong dependence of the co-assembly process on fCP-PEG due to thermodynamic limit of incorporating one CPN in one PMMA microdomain, as well as the kinetic pathway in which favorable PEG-solvent interaction helps to disperse CPNs and thus lowers the activation energy barrier of the system. This study presents critical insights in guided assemblies of functional building blocks within nanoscopic frameworks. DOE-EFRC-Gas Separation, Army Research Office.

  5. Study on the Matching Relationship between Polymer Hydrodynamic Characteristic Size and Pore Throat Radius of Target Block S Based on the Microporous Membrane Filtration Method

    Directory of Open Access Journals (Sweden)

    Li Yiqiang


    Full Text Available The concept of the hydrodynamic characteristic size of polymer was proposed in this study, to characterize the size of aggregates of many polymer molecules in the polymer percolation process. The hydrodynamic characteristic sizes of polymers used in the target block S were examined by employing microporous membrane filtration method, and the factors were studied. Natural core flow experiments were conducted in order to set up the flow matching relationship plate. According to the flow matching plate, the relationship between the hydrodynamic characteristic size of polymer and pore throat radius obtained from core mercury injection data was found. And several suitable polymers for different reservoirs permeability were given. The experimental results of microporous membrane filtration indicated that the hydrodynamic characteristic size of polymer maintained a good nonlinear relationship with polymer viscosity; the value increased as the molecular weight and concentration of the polymer increased and increased as the salinity of dilution water decreased. Additionally, the hydrodynamic characteristic size decreased as the pressure increased, so the hydrodynamic characteristic size ought to be determined based on the pressure of the target block. In the core flow studies, good matching of polymer and formation was identified as polymer flow pressure gradient lower than the fracture pressure gradient of formation. In this case, good matching that was the pore throat radius should be larger than 10 times the hydrodynamic characteristic size of polymer in this study. Using relationship, more matching relationship between the hydrodynamic characteristic sizes of polymer solutions and the pore throat radius of target block was determined.

  6. Electron Transfer of Myoglobin Immobilized in Au Electrodes Modified with a RAFT PMMA-Block-PDMAEMA Polymer

    Directory of Open Access Journals (Sweden)

    Carla N. Toledo


    Full Text Available Myoglobin was immobilized with poly(methyl methacrylate-block-poly[(2-dimethylaminoethyl methacrylate]PMMA-block-PDMAEMA polymer synthesized by reversible addition-fragmentation chain transfer technique (RAFT. Cyclic voltammograms gave direct and slow quasireversible heterogeneous electron transfer kinetics between Mb-PMMA-block-PDMAEMA modified electrode and the redox center of the protein. The values for electron rate constant (Ks and transfer coefficient (α were 0.055±0.01·s−1 and 0.81±0.08, respectively. The reduction potential determined as a function of temperature (293–328 K revealed a value of reaction center entropy of ΔS0 of 351.3±0.0002 J·mol−1·K−1 and enthalpy change of -76.8±0.1 kJ·mol−1, suggesting solvent effects and charge ionization atmosphere involved in the reaction parallel to hydrophobic interactions with the copolymer. The immobilized protein also exhibits an electrocatalytical response to reduction of hydrogen peroxide, with an apparent Km of 114.7±58.7 μM. The overall results substantiate the design and use of RAFT polymers towards the development of third-generation biosensors.

  7. 5,10-linked naphthodithiophenes as the building block for semiconducting polymers (United States)

    Osaka, Itaru; Komatsu, Koki; Koganezawa, Tomoyuki; Takimiya, Kazuo


    We present new semiconducting polymers incorporating naphtho[1, 2-b:5, 6-b‧] dithiophene (NDT3) and naphtho[2, 1-b:6, 5-b‧] dithiophene (NDT4), which are linked at the naphthalene positions, in the polymer backbone. It is interesting that the trend in the ordering structure and thus charge transport properties are quite different from what were observed in the isomeric polymers where the NDT3 and NDT4 cores are linked at the thiophene α-positions. In the thiophene-linked NDT system, the NDT3-based polymer (PNDT3BT) gave the better ordering in thin films and thus the high charge carrier mobility compared to the NDT4-based polymer (PNDT4BT). In the meantime, in the naphthalene-linked NDT system, the NDT4-based polymer (PNDT4iBT) provided the superior properties. Considering that PNDT4iBT has relatively low highest occupied molecular orbital (HOMO) energy level (-5.2 eV) and moderately high mobilities in the order of 10-2 cm2 V-1 s-1, the NDT4 core, when linked at the naphthalene positions, can be a good building unit for the development of high-performance semiconducting polymers for both organic field-effect transistors and photovoltaic devices.

  8. Effect of ultrasonic pretreatment on emulsion polymerization of styrene. (United States)

    Nagatomo, Daichi; Horie, Takafumi; Hongo, Chizuru; Ohmura, Naoto


    This study investigated the effect of pretreatment of ultrasonic irradiation on emulsion polymerization of styrene to propose a process intensification method which gives high conversion, high reaction rate, and high energy efficiency. The solution containing styrene monomer was irradiated by a horn mounted on the ultrasonic transducer with the diameter of 5mm diameter and the frequency of 28 kHz before starting polymerization. The pretreatment of ultrasound irradiation as short as 1 min drastically improved monomer dispersion and increased reaction rate even under the agitation condition with low rotational speed of impeller. Furthermore, the ultrasonic pretreatment resulted in higher monomer concentration in polymer particles and produced larger polymer particles than conventional polymerization without ultrasonic pretreatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Block copolymer micelle coronas as quasi-two-dimensional dilute or semidilute polymer solutions

    DEFF Research Database (Denmark)

    Svaneborg, C.; Pedersen, J.S.


    Chain-chain interactions in a corona of polymers tethered to a spherical core under good solvent conditions are studied using Monte Carlo simulations. The total scattering function of the corona as well as different partial contributions are sampled. By combining the different contributions...... in a self-consistent approach, it is demonstrated that the corona can be regarded as a quasi-two-dimensional polymer solution, with a concentration dependence analogous to that of an ordinary polymer solution. Scattering due to the corona profile and density fluctuation correlations are separated...

  10. Grafting of styrene onto polypropylene membranes

    Energy Technology Data Exchange (ETDEWEB)

    Zen, Heloisa A.; Geraldes, Adriana N.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], E-mail:


    The grafting of styrene onto polypropylene (PP) by simultaneous radiation was carried out. The effects of absorbed dose and the pos radiation period on the grafting yield were investigated. The experiment comprised PP films with 40{mu}m thickness exposed to gamma ionizing radiation at room temperature and nitrogen atmosphere. The films were immersed in styrene/toluene and then irradiated at total dose of 40, 80 and 100 kGy. After irradiation the samples were evaluated at periods of 0, 7, 14, 21 and 28 days at room temperature in order to observe the behavior of grafting degree. Structural, chemical changes and surface morphologies of the modified PP films were characterized by infrared spectroscopic analysis (FTIR), differential scanning calorimetry analysis (DSC), thermogravimetric analysis (TGA) and the degree of grafting (DOG) was gravimetrically determined. The simultaneous radiation indicated the dependency of the percent graft on the absorbed dose. The DOG values are higher when the film was submitted at 100 kGy dose. The thermal stability shows a decrease in the degradation temperature of the modified samples in comparison with the pure polymer. (author)

  11. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan


    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Organic Polymers Modified with Inorganic Polyhedra

    National Research Council Canada - National Science Library

    Haddad, Timothy


    ...) macromers into organic polymers. These hybrid inorganic/organic thermoplastics based on styrenes, acrylics, imides, norbornenes or siloxanes, are reinforced by covalently linking monodisperse inorganic POSS clusters to the polymer backbone...

  13. Investigation of the use of recycled polymer-modified asphalt in asphaltic concrete pavements. (United States)


    This report presents issues associated with recycling polymer modified asphalt cements (PMACs), particularly blending aged PMAC with new PMAC. A styrene-butadiene-styrene (SBS) PMAC was selected and graded using the Superpave Performance Grading (PG)...

  14. Technoeconomic evaluation of bio-based styrene production by engineered Escherichia coli. (United States)

    Claypool, Joshua T; Raman, D Raj; Jarboe, Laura R; Nielsen, David R


    Styrene is an important commodity chemical used in polymers and resins, and is typically produced from the petrochemical feedstocks benzene and ethylene. Styrene has recently been produced biosynthetically for the first time using engineered Escherichia coli, and this bio-based route may represent a lower energy and renewable alternative to petroleum-derived styrene. However, the economics of such an approach has not yet been investigated. Using an early-stage technoeconomic evaluation tool, a preliminary economic analysis of bio-based styrene from C(6)-sugar feedstock has been conducted. Owing to styrene's limited water solubility, it was assumed that the resulting fermentation broth would spontaneously form two immiscible liquid phases that could subsequently be decanted. Assuming current C(6) sugar prices and industrially achievable biokinetic parameter values (e.g., product yield, specific growth rate), commercial-scale bio-based styrene has a minimum estimated selling price (MESP) of 1.90 USD kg(-1) which is in the range of current styrene prices. A Monte Carlo analysis revealed a potentially large (0.45 USD kg(-1)) standard deviation in the MESP, while a sensitivity analysis showed feedstock price and overall yield as primary drivers of MESP.

  15. Tuning of polymeric nanoparticles by coassembly of thermoresponsive polymers and a double hydrophilic thermoresponsive block copolymer

    Czech Academy of Sciences Publication Activity Database

    Zhang, Q.; Voorhaar, L.; Filippov, Sergey K.; Yesil, B. F.; Hoogenboom, R.


    Roč. 120, č. 20 (2016), s. 4635-4643 ISSN 1520-6106 R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : nanoparticles * thermoresponsive polymers * self-assembly Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.177, year: 2016

  16. Production in Pichia pastoris of protein-based polymers with small heterodimer-forming blocks

    NARCIS (Netherlands)

    Domeradzka, N.E.; Werten, M.W.T.; Vries, de R.J.; Wolf, de F.A.


    Some combinations of leucine zipper peptides are capable of forming a-helical heterodimeric coiled coils with very high affinity. These can be used as physical cross-linkers in the design of protein-based polymers that form supramolecular structures, for example hydrogels, upon mixing solutions

  17. Performance Analysis of Styrene Butadiene Rubber-Latex on Cement Concrete Mixes.


    Er. Kapil Soni; Dr. Y.P Joshi


    To improve the performance of concrete, polymers are mixed with concrete. It has been observed that polymer-modified concrete (PMC) is more durable than conventional concrete due to superior strength and high durability. In this research, effect of Styrene-Butadiene Rubber (SBR) latex on compressive strength and flexural strength of concrete has been studied and also the optimum polymer (SBR-Latex) content for concrete is calculated. This research was carried out to establish t...

  18. A Thieno[3,2-b][1]benzothiophene Isoindigo Building Block for Additive- and Annealing-Free High-Performance Polymer Solar Cells

    KAUST Repository

    Yue, Wan


    A novel photoactive polymer with two different molecular weights is reported, based on a new building block: thieno[3,2-b][1]benzothiophene isoindigo. Due to the improved crystallinity, optimal blend morphology, and higher charge mobility, solar-cell devices of the high-molecular-weight polymer exhibit a superior performance, affording efficiencies of 9.1% without the need for additives, annealing, or additional extraction layers during device fabrication.

  19. Dynamic Self-Consistent Field Theories for Polymer Blends and Block Copolymers (United States)

    Kawakatsu, Toshihiro

    Understanding the behavior of the phase separated domain structures and rheological properties of multi-component polymeric systems require detailed information on the dynamics of domains and that of conformations of constituent polymer chains. Self-consistent field (SCF) theory is a useful tool to treat such a problem because the conformation entropy of polymer chains in inhomogeneous systems can be evaluated quantitatively using this theory. However, when we turn our attention to the dynamic properties in a non-equilibrium state, the basic assumption of the SCF theory, i.e. the assumption of equilibrium chain conformation, breaks down. In order to avoid such a difficulty, dynamic SCF theories were developed. In this chapter, we give a brief review of the recent developments of dynamic SCF theories, and discuss where the cutting-edge of this theory is.

  20. Fluorinated building blocks for next-generation polymer electrolyte membrane fuel cells

    NARCIS (Netherlands)

    Wadekar, M.N.


    The purpose of this thesis is to design, create and study basic building blocks for the construction of self-assembled nanostructured electrodes and membranes for PEMFC. The research described deals with the synthesis of polymerizable fluorosurfactant (1) and its non-polymerizable analogue (2) and

  1. Lithium Polymer Electrolytes Based On PMMA / PEG And Penetrant Diffusion In Kraton Penta-Block Ionomer (United States)

    Meng, Yan

    The study of diffusion in polymeric material is critical to many research fields and applications, such as polymer morphology, protective coatings (paints and varnishes), separation membranes, transport phenomena, polymer electrolytes, polymer melt, and controlled release of drugs from polymer carriers [1-9]. However, it is still a challenge to understand, predict and control the diffusion of molecules and ions of different sizes in polymers [2]. This work studied the medium to long range diffusion of species (i.e., ions and molecules) in solid polymer electrolytes based on poly(ethylene glycol)/poly(methyl methacrylate) (PEG/PMMA) for Li-based batteries, and polymeric permselective membranes via pulsed-field gradient NMR and a.c. impedance. Over the past decades polymer electrolytes have attracted much attention because of their promising technological application as an ion-conducting medium in solid-state batteries, fuel cells, electrochromic displays, and chemical sensors [10, 11]. However, despite numerous studies related to ionic transport in these electrolytes the understanding of the migration mechanism is still far from being complete, and progress in the field remains largely empirical [10, 12-15]. Among various candidates for solid polymer electrolyte (SPE) material, the miscible polymer pair, poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA), is an attractive one, because there is a huge difference in mobility between PEO and PMMA in their blends, and PEO chains remain exceptionally mobile in the blend even at temperature below the glass transition temperature of the blend [ 16]. Thus the mechanical strength and dimensional stability is maintained by PMMA component, while the chain motions or rearrangements of the PEO component virtually contribute to the ion transport [17]. The current work prepared two types of SPE based on poly(ethylene glycol) (PEG) /PMMA (40/60 by weight) for Li-based batteries: lithium bis(trifluoromethylsulfonylimide) (Li

  2. Design of block copolymer membranes using segregation strength trend lines

    KAUST Repository

    Sutisna, Burhannudin


    Block copolymer self-assembly and non-solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution and high porosity. The method has the potential to be used with a broad range of tailor-made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene-b-ethylene oxide) diblocks and extended it to newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS-b-P2VP-b-PEO membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS), which revealed a hexagonal micelle order with domain spacing clearly correlated to the membrane interpore distances.

  3. The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes (United States)

    Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

    Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

  4. Environmentally benign electroless nickel plating using supercritical carbon-dioxide on hydrophilically modified acrylonitrile-butadiene-styrene (United States)

    Tengsuwan, Siwach; Ohshima, Masahiro


    Electroless Ni-P plating using supercritical carbon dioxide (scCO2) in conjunction with copolymer-based hydrophilic modification was applied to an acrylonitrile-butadiene-styrene (ABS) substrate. The surface of ABS substrate was hydrophilically modified by blending with a multi-block copolymer, poly(ether-ester-amide)s (PEEA), in injection molding process. The substrate was then impregnated with Pd(II)-hexafluoroacetylacetonate, Pd(hfa)2, using scCO2, followed by the electroless plating reaction. ABS/PEEA substrates with different PEEA to ABS blend ratios and different volume ratios of butadiene to the styrene-acrylonitrile copolymer (SAN) matrix were prepared to investigate how the dispersed PEEA and butadiene domains affected the blend morphology and the adhesive strength of the plating metal-to-polymer contact. Increasing the PEEA copolymer to ABS blend ratio increased the mass transfer rate of the plating solution in the ABS substrate. Consequently, the metal-polymer composite layer became thicker, which increased the adhesive strength of the metal-to-polymer contact because of the anchoring effect. The butadiene domains appeared to attract the Pd catalyst precursor, and thus, the proportion of butadiene in the ABS matrix also affected the adhesive strength of the contact between the metal layer and the substrate. The ABS substrate was successfully plated with a Ni-P metal layer with an average adhesive strength of 9.1 ± 0.5 N cm-1 by choosing appropriate ABS/PEEA blend ratios and a Pd(hfa)2 concentration.

  5. Computational Modeling of Polystyrene-b-(ethylene-co-butylene)-b-styrene and Mineral Oil Gels and Nanocomposites (United States)

    Chantawansri, T. L.; Berg, M.; Mrozek, R.; Stokes, K.; Henz, B.; Chung, P.; Beyer, F.; Lenhart, J.; Andzelm, J. W.


    There has been substantial interest in thermoplastic elastomer (TPE) gels composed of poly(styrene-b-(ethylene-co-butylene)-b-styrene)(SEBS) and hydrocarbon oils. Although the effects of adding nanoparticles on TPE gels is relatively unexplored, research in polymer nanocomposites have shown that the addition of nanoparticles enhanced physical properties. The microstructure of such a system is dependent on a variety of parameters such as block copolymer and nanoparticle concentrations, temperature, nanoparticle size, and nanoparticle interaction; thus to perform an extensive study of phase space, mesoscale modeling should be used in conjunction with the experimentation. To complement our experimental system, mesoscale modeling of this TPE gel and the corresponding nanocomposite are preformed using dynamic density functional theory and self consistent field theory through Materials Studio, where morphology of the system is studied as a function of various parameters and conditions. The validity of the computational methods has been confirmed for a number of experimental results, and subsequently has been used to explore a larger design space than is accessible solely through experimental methods.

  6. Styrene-based shape memory foam: fabrication and mathematical modeling (United States)

    Yao, Yongtao; Zhou, Tianyang; Qin, Chao; Liu, Yanju; Leng, Jinsong


    Shape memory polymer foam is a promising kind of structure in the biomedical and aerospace field. Shape memory styrene foam with uniform and controlled open-cell structure was successfully fabricated using a salt particulate leaching method. Shape recovery capability exists for foam programming in both high-temperature compression and low-temperature compression (Shape recovery properties such as shape fixing property and shape recovery ratio were also characterized. In order to provide guidance for the future fabrication of shape memory foam, the theories of Gibson and Ashby as well as differential micromechanics theory were applied to predict Young’s modulus and the mechanical behavior of SMP styrene foams during the compression process.

  7. Where Scattering and Computations Meet: Structure and Dynamics of Ionic Co-Polymers (United States)

    Perahia, Dvora


    Ion transporting polymers constitute vital components in clean energy generation and storage devices including electrolytic media in fuel cells and ion conducting separators in batteries. While different polymers are currently in use, achieving controlled ion transport and storage ability while retaining mechanical and chemical stability remains a challenge: under the conditions which optimize the transport and storage for specific application, either mechanical or chemical stabilities are compromised. Designing block-co-polymers with ion transporting blocks bound to blocks that enhance mechanical and chemical stability would mitigate the challenge. Tailoring block copolymers with blocks that exhibit various desired properties, results in a new set of open questions that pertain to new complex materials including defining the phase diagram and understanding the interfacial regions of the muliblocks. Here we present the first molecular-level computational insight of the behavior of a pentablock, A-B-C-B-A, co-polymer that consists of an A block of poly(t-butyl-styrene), a B block of ethylene-r-propylene and a C block of a randomly sulfonated styrene, in solution in comparison with neutron scattering data. Neutron studies have shown that in hydrophobic solvents this pentablock forms elongated micelles in dilute solutions where the ionic block dominates the solution structure. These studies provide ensemble average of structure and properties. The computational studies provided further molecular-level insight. Here we will discuss the interrelations between scattering results and computational studies to provide remarkable understanding of a complex ionic system. Pathways to advance this molecular understanding to an actual membrane will be then discussed. We thank DOE contact DE-FGO2-12ER46843 for support of this work.

  8. Development of Styrene-Grafted Polyurethane by Radiation-Based Techniques

    Directory of Open Access Journals (Sweden)

    Jin-Oh Jeong


    Full Text Available Polyurethane (PU is the fifth most common polymer in the general consumer market, following Polypropylene (PP, Polyethylene (PE, Polyvinyl chloride (PVC, and Polystyrene (PS, and the most common polymer for thermosetting resins. In particular, polyurethane has excellent hardness and heat resistance, is a widely used material for electronic products and automotive parts, and can be used to create products of various physical properties, including rigid and flexible foams, films, and fibers. However, the use of polar polymer polyurethane as an impact modifier of non-polar polymers is limited due to poor combustion resistance and impact resistance. In this study, we used gamma irradiation at 25 and 50 kGy to introduce the styrene of hydrophobic monomer on the polyurethane as an impact modifier of the non-polar polymer. To verify grafted styrene, we confirmed the phenyl group of styrene at 690 cm−1 by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR and at 6.4–6.8 ppm by 1H-Nuclear Magnetic Resonance (1H-NMR. Scanning Electron Microscope (SEM, X-ray Photoelectron Spectroscopy (XPS, Thermogravimetric Analysis (TGA and contact angle analysis were also used to confirm styrene introduction. This study has confirmed the possibility of applying high-functional composite through radiation-based techniques.

  9. Solvent- and Halogen-Free Modification of Biobased Polyphenols to Introduce Vinyl Groups: Versatile Aromatic Building Blocks for Polymer Synthesis. (United States)

    Duval, Antoine; Avérous, Luc


    Various biobased polyphenols (lignins and condensed tannins) were derivatized with vinyl ethylene carbonate, a functional cyclic carbonate, to obtain multifunctional aromatic polymers bearing vinyl groups. The reaction was optimized on a condensed tannin and soda lignin. In both cases, full conversion of the phenol groups was achieved in only 1 h at 150 °C without solvent and with K2 CO3 as a cheap and safe catalyst. This reaction was later applied to other condensed tannins and technical lignins (Kraft and organosolv), showing only little dependence on the chemical structure of the polyphenols. The obtained derivatives were thoroughly characterized by 1 H and 31 P NMR spectroscopy, FTIR spectroscopy, and size-exclusion chromatography. The developed method was compared with previously published protocols for the introduction of vinyl groups on lignin, and shows promising advances toward the modification of biobased polyphenols according to green chemistry principles. The obtained macromolecules show great potential as highly versatile biobased aromatic building blocks for the synthesis of polymers through, for example, radical, metathesis, or thiol-ene reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Dynamics of Lithium Polymer Electrolytes using X-ray Photon Correlation Spectroscopy and Rheology (United States)

    Oparaji, Onyekachi; Narayanan, Suresh; Sandy, Alec; Hallinan, Daniel, Jr.

    Polymer electrolytes are promising materials for high energy density rechargeable batteries. Battery fade can be caused by structural evolution in the battery electrode and loss of electrode/electrolyte adhesion during cycling. Both of these effects are dependent on polymer mechanical properties. In addition, cycling rate is dictated by the ion mobility of the polymer electrolyte. Lithium ion mobility is expected to be strongly coupled to polymer dynamics. Therefore, we investigate polymer dynamics as a function of salt concentration using X-ray Photon Correlation Spectroscopy (XPCS) and rheology. We report the influence of lithium salt concentration on the structural relaxation time (XPCS) and stress relaxation time (rheology) of high molecular weight poly(styrene - ethylene oxide) block copolymer membranes.

  11. Rich Phase Behavior of Sphere-Forming Asymmetric ABA'C Block Copolymer Melts (United States)

    Chanpuriya, Sid; Arora, Akash; Kim, Kyungtae; Dorfman, Kevin; Bates, Frank

    Motivated by self-consistent field theory simulations, the effect of ABA' corona block length asymmetry on the phase behavior of ABA'C-type tetrablock terpolymers has been examined. The chosen model system, poly(styrene)- b-poly(isoprene)- b-poly(styrene)- b-poly(ethylene oxide) (SIS'O), has been characterized using a combination of small-angle X-ray scattering, transmission electron microscopy, and dynamic mechanical spectroscopy. Asymmetric SIS'O tetrablocks reveal a rich variety of sphere-forming phases over compositions and molecular weights where symmetric SISO polymers formed only hexagonally oriented cylinders. These include FCC, HCP, and complex symmetries such as the Frank-Kasper σ and A15 phases. NSF Award 1333669.

  12. Functionalized Nanochannels from Self-Assembled and Photomodified Poly(Styrene-b-Butadiene-b-Styrene). (United States)

    Sutisna, Burhannudin; Polymeropoulos, George; Musteata, Valentina; Sougrat, Rachid; Smilgies, Detlef-M; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana P


    Membranes are prepared by self-assembly and casting of 5 and 13 wt% poly(styrene-b-butadiene-b-styrene) (PS-b-PB-b-PS) copolymers solutions in different solvents, followed by immersion in water or ethanol. By controlling the solution-casting gap, porous films of 50 and 1 µm thickness are obtained. A gradient of increasing pore size is generated as the distance from the surface increased. An ordered porous surface layer with continuous nanochannels can be observed. Its formation is investigated, by using time-resolved grazing incident small angle X-ray scattering, electron microscopy, and rheology, suggesting a strong effect of the air-solution interface on the morphology formation. The thin PS-b-PB-b-PS ordered films are modified, by promoting the photolytic addition of thioglycolic acid to the polybutadiene groups, adding chemical functionality and specific transport characteristics on the preformed nanochannels, without sacrificing the membrane morphology. Photomodification increases fivefold the water permeance to around 2 L m(-2) h(-1) bar(-1) , compared to that of the unmodified one. A rejection of 74% is measured for methyl orange in water. The membranes fabrication with tailored nanochannels and chemical functionalities can be demonstrated using relatively lower cost block copolymers. Casting on porous polyacrylonitrile supports makes the membranes even more scalable and competitive in large scale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

    KAUST Repository

    Dorin, Rachel Mika


    Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

  14. Influence of morphology on electrical breakdown characteristics of ethylen-styrene copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, Masaaki; Matsuo, Katsuya; Oki, Yoshimichi; Hozumi, Naohiro; Harashige, Masahiro


    For developing the insulating material of ethylene-styrene copolymer to be applicable to 500 Kv electric cable, a study was conducted on the relation between higher order molecular structure and breakdown characteristics of insulator. The experiment was composed of measurement of intensity of electric field at breakdown, of its dependency on the wave shape of voltage, of melting behavior of crystal by differential scanning calorimeter, of degree of crystallinity by x-ray diffraction, and of the observation by transmission type electronic microscope. As the result of experiment, dependency of crystallinity on styrene content, linear correlation of total absorbed heat with ethylene content, and of hardness and styrene content, were shown as graphs. Relation between the intensity of breakdown electric field and styrene content was approximated by two broken straight lines. As the consideration, it was obtained that the breakdown occurred at the weak point of polyethylene structure, that the intensity of breakdown electric field was increased proportionally with styrene content, and that, for achieving higher breakdown voltage by increasing the energy absorbing capacity of benzene ring, randomly copolymerized copolymer with uniform dispersion of styrene molecule was better than graft polymer of the same components. (13 figs, 8 refs)

  15. Ionomeric membranes based on partially sulfonated poly(styrene) : synthesis, proton conduction and methanol permeation

    NARCIS (Netherlands)

    Picchioni, F.; Tricoli, V.; Carretta, N.


    Homogeneuosly sulfonated poly(styrene) (SPS) was prepared with various concentration of sulfonic acid groups in the base polymer. Membranes cast from these materials were investigated in relation to proton conductivity and methanol permeability in the temperature range from 20°C to 60°C. It was

  16. Poly[(3-hexylthiophene-block-(3-semifluoroalkylthiophene] for Polymer Solar Cells

    Directory of Open Access Journals (Sweden)

    Takeshi Toru


    Full Text Available We report the synthesis of poly[(3-hexylthiophene-block-(3-(4,4,5,5,6,6,7,7,7-nonafluoroheptylthiophene], P(3HT-b-3SFT, carried out by the Grignard Metathesis Method (GRIM. The copolymers composition was determined by 1H and 19F NMR spectroscopies, and gel permeation chromatography (GPC. The thin films of P(3HT‑b‑3SFT were investigated by ultraviolet-visible absorption spectroscopy and atomic force microscopy (AFM. We also fabricated bulk-hetero junction (BHJ solar cells based on blends of P(3HT-b-3SFT and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM. Although the composition ratio of P3SFT in P(3HT-b-3SFT was low, the influence of P3SFT on the morphology and properties of solar cells was significant. The annealing process for the BHJ solar cells induced the formation of large domains and led to poor solar cell performance. The BHJ solar cells, based on PCBM and P(3HT-b-3SFT, prepared by the non-annealing process, had a maximum power conversion efficiency of 0.84% under 100 mW/cm2 (AM 1.5 solar illumination in air.

  17. Devulcanization of styrene butadiene (SBR) waste tire by controlled oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rios, Rachel R.V.A.; Gontijo, Manuela; Ferraz, Vany P.; Lago, Rochel M.; Araujo, Maria Helena [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica]. E-mail:


    This work describes the devulcanization of vulcanized SBR (Styrene Butadiene Rubber) based on controlled oxidation with nitric acid. IR, {sup 1}H and {sup 13}C-NMR, CHN elemental analyses, TG, GPC and TPD-MS (Temperature Programmed Decomposition-Mass Spectrometry) experiments suggest that nitric acid promotes two processes: devulcanization by oxidation of the sulfide crosslinks and oxidation of the carbon framework leading to the formation of -COOH and -NO{sub 2} groups. Under aggressive conditions (HNO{sub 3}, reflux) the polymer chain is strongly oxidized and fragmented to a highly oxygenated low molecular weight fraction, which is soluble in water. (author)

  18. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan

    National Research Council Canada - National Science Library

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3‐butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin ( ABS ) and acrylonitrile–styrene resin...

  19. Hydrothermal Synthesis and Processing of Barium Titanate Nanoparticles Embedded in Polymer Films. (United States)

    Toomey, Michael D; Gao, Kai; Mendis, Gamini P; Slamovich, Elliott B; Howarter, John A


    Barium titanate nanoparticles embedded in flexible polymer films were synthesized using hydrothermal processing methods. The resulting films were characterized with respect to material composition, size distribution of nanoparticles, and spatial location of particles within the polymer film. Synthesis conditions were varied based on the mechanical properties of the polymer films, ratio of polymer to barium titanate precursors, and length of aging time between initial formulations of the solution to final processing of nanoparticles. Block copolymers of poly(styrene-co-maleic anhydride) (SMAh) were used to spatially separate titanium precursors based on specific chemical interactions with the maleic anhydride moiety. However, the glassy nature of this copolymer restricted mobility of the titanium precursors during hydrothermal processing. The addition of rubbery butadiene moieties, through mixing of the SMAh with poly(styrene-butadiene-styrene) (SBS) copolymer, increased the nanoparticle dispersion as a result of greater diffusivity of the titanium precursor via higher mobility of the polymer matrix. Additionally, an aminosilane was used as a means to retard cross-linking in polymer-metalorganic solutions, as the titanium precursor molecules were shown to react and form networks prior to hydrothermal processing. By adding small amounts of competing aminosilane, excessive cross-linking was prevented without significantly impacting the quality and composition of the final barium titanate nanoparticles. X-ray diffraction and X-ray photoelectron spectroscopy were used to verify nanoparticle compositions. Particle sizes within the polymer films were measured to be 108 ± 5 nm, 100 ± 6 nm, and 60 ± 5 nm under different synthetic conditions using electron microscopy. Flexibility of the films was assessed through measurement of the glass transition temperature using dynamic mechanical analysis. Dielectric permittivity was measured using an impedance analyzer.

  20. Cell Penetrating Polymers Containing Guanidinium Trigger Apoptosis in Human Hepatocellular Carcinoma Cells unless Conjugated to a Targeting N-Acetyl-Galactosamine Block. (United States)

    Tan, Zhe; Dhande, Yogesh K; Reineke, Theresa M


    A series of 3-guanidinopropyl methacrylamide (GPMA)-based polymeric gene delivery vehicles were developed via aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers have been evaluated for their cellular internalization ability, transfection efficiency, and cytotoxicity. Two homopolymers: P(GPMA 20 ), P(GPMA 34 ), were synthesized to study the effect of guanidium polymer length on delivery efficiency and toxicity. In addition, an N-acetyl-d-galactosamine (GalNAc)-based hydrophilic block was incorporated to produce diblock polymers, which provides a neutral hydrophilic block that sterically protects plasmid-polymer complexes (polyplexes) from colloidal aggregation and aids polyplex targeting to hepatocytes via binding to asialoglycoprotein receptors (ASGPRs). Polyplexes formed with P(GPMA x ) (x = 20, 34) homopolymers were shown to be internalized via both energy-dependent and independent pathways, whereas polyplexes formed with block polymers were internalized through endocytosis. Notably, P(GPMA x ) polyplexes enter cells very efficiently but are also very toxic to human hepatocellular carcinoma (HepG2) cells and triggered cell apoptosis. In comparison, the presence of a carbohydrate block in the polymer structures reduced the cytotoxicity of the polyplex formulations and increased gene delivery efficiency with HepG2 cells. Transfection efficiency and toxicity studies were also carried out with HEK 293T (human embryonic kidney) cells for comparison. Results showed that polyplexes formed with the P(GPMA x ) homopolymers exhibit much higher transfection efficiency and lower toxicity with HEK 293T cells. The presence of the carbohydrate block did not further increase transfection efficiency in comparison to the homopolymers with HEK 293T cells, likely due to the lack of ASGPRs on the HEK 293T cell line. This study revealed that although guanidinium-based polymers have high membrane permeability, their application as plasmid

  1. Reversible pH Stimulus-Response Material Based on Amphiphilic Block Polymer Self-Assembly and Its Electrochemical Application

    Directory of Open Access Journals (Sweden)

    Tianyi Wang


    Full Text Available Stimulus-responsive microporous solid thin films were successfully fabricated by simple molecular self-assembly via an amphiphilic block polymer, polystryene–b–polyacrylic acid (PS–b–PAA. The solid thin films exhibit different surface morphologies in response to external stimuli, such as environments with different pH values in aqueous solutions. The experiments have successfully applied atomic force microscope (AFM technology to observe in-situ surface morphological changes. There is a reversible evolution of the microstructures in buffer solutions over a pH range of 2.4–9.2. These observations have been explained by positing that there is no conventional PAA swelling but that the PAA chains in the micropores stretch and contract with changes in the pH of the solution environment. The hydrophobicity of the solid thin film surface was transformed into super-hydrophilicity, as captured by optical contact angle measurements. The stimulus-responsive dynamics of pore sizes was described by a two-stage mechanism. A promising electrochemical application of this film is suggested via combination with an electrochemical impedance technique. This study is aimed at strategies for the functionalization of stimulus-responsive microporous solid thin films with reversible tunable surface morphologies, and exploring new smart materials with switch-on/switch-off behavior.

  2. Characterisation of recycled acrylonitrile-butadiene-styrene and high-impact polystyrene from waste computer equipment in Brazil. (United States)

    Hirayama, Denise; Saron, Clodoaldo


    Polymeric materials constitute a considerable fraction of waste computer equipment and polymers acrylonitrile-butadiene-styrene and high-impact polystyrene are the main thermoplastic polymeric components found in waste computer equipment. Identification, separation and characterisation of additives present in acrylonitrile-butadiene-styrene and high-impact polystyrene are fundamental procedures to mechanical recycling of these polymers. The aim of this study was to evaluate the methods for identification of acrylonitrile-butadiene-styrene and high-impact polystyrene from waste computer equipment in Brazil, as well as their potential for mechanical recycling. The imprecise utilisation of symbols for identification of the polymers and the presence of additives containing toxic elements in determinate computer devices are some of the difficulties found for recycling of acrylonitrile-butadiene-styrene and high-impact polystyrene from waste computer equipment. However, the considerable performance of mechanical properties of the recycled acrylonitrile-butadiene-styrene and high-impact polystyrene when compared with the virgin materials confirms the potential for mechanical recycling of these polymers. © The Author(s) 2015.

  3. Helbredsrisici ved eksponering for styren i glasfiberplastindustrien

    DEFF Research Database (Denmark)

    Kolstad, Henrik Albert; Ebbehøj, Nielse; Bonde, Jens Peter


    This is a summary of the health risks of occupational styrene exposure based on recent reviews. We conclude about the exposure levels that there is strong evidence that styrene causes acute irritation of eyes and respiratory tract above 25 ppm, genotoxic effects above 10 ppm, and persistent nervous...... or relevant exposure levels. We recommend reconsideration of the current Danish threshold limit value of 25 ppm, biological monitoring of styrene exposed workers, and epidemiological analyses of styrene exposure levels and long-term health effects among employees of the Danish reinforced plastics industry....... system effects with for instance reduced psychological performance, colour discrimination and hearing level following long-term styrene exposure above 10 ppm. There is moderate evidence of a causal association with cancer, but data are not sufficient to allow us to pinpoint specific cancers at risk...

  4. Acquired dyschromatopsia among styrene-exposed workers. (United States)

    Gobba, F; Galassi, C; Imbriani, M; Ghittori, S; Candela, S; Cavalleri, A


    We investigated the occurrence of color vision loss in 75 styrene-exposed workers and in 60 referents. Color vision was evaluated by adopting the Lanthony D 15 desaturated panel, a test specifically suited to detect mild acquired dyschromatopsia. The results of the test were expressed as Color Confusion Index. Styrene exposure was evaluated with both environmental and biological monitoring. Airborne levels of the solvent were 3.2 to 549.5 mg/m3. In styrene-exposed workers color vision was significantly impaired when compared with referents matched for age. A significative correlation was found between environmental and urinary levels of styrene and Color Confusion Index excluding the influence of age in multiple regression analysis, indicating the possibility of a dose-effect relationship. The findings suggest that styrene can induce an early appearance of a dose-dependent color vision loss.

  5. Helbredsrisici ved eksponering for styren i glasfiberplastindustrien

    DEFF Research Database (Denmark)

    Kolstad, Henrik Albert; Ebbehøj, Nielse; Bonde, Jens Peter


    or relevant exposure levels. We recommend reconsideration of the current Danish threshold limit value of 25 ppm, biological monitoring of styrene exposed workers, and epidemiological analyses of styrene exposure levels and long-term health effects among employees of the Danish reinforced plastics industry.......This is a summary of the health risks of occupational styrene exposure based on recent reviews. We conclude about the exposure levels that there is strong evidence that styrene causes acute irritation of eyes and respiratory tract above 25 ppm, genotoxic effects above 10 ppm, and persistent nervous...... system effects with for instance reduced psychological performance, colour discrimination and hearing level following long-term styrene exposure above 10 ppm. There is moderate evidence of a causal association with cancer, but data are not sufficient to allow us to pinpoint specific cancers at risk...

  6. New styrene-b-isobutylene-b-styrene (SIBS) glaucoma drainage implant (United States)

    Orozco, Marcia A.; Acosta, Ana C.; Espana, Edgar M.; Pinchuk, Leonard; Weber, Bruce; Davis, Stewart; Arrieta, Esdras; Dubovy, Sander; Fantes, Francisco; Aly, Mohamed; Zhou, Yonghua; Parel, Jean-Marie


    Purpose: To design and test the Miami-InnFocus Drainage Implant (MiDi) as a glaucoma shunt that is biocompatible, flexible, and significantly smaller than existing commercial implants in order to prevent postoperative hypotony, inflammation, scarring, erosion, and extrusion. Methods: A new biomaterial composed of styrene-b-isobutylene-b-styrene (SIBS) was used in a novel design for a glaucoma drainage implant. The implant consists of a tube 11mm long with an inner diameter of 70, 100, and 150 μm and outer diameter of 250 μm with a 1mm2 tab located 4.5mm from the proximal tip to prevent migration. The device was implanted in 15 New Zealand White rabbits for biocompatibility and efficacy testing. A similarly designed implant made of polydimethylsiloxane was implanted in 6 other animals as a pseudo-control. Typical GDI implantation technique was modified for this device. The proximal end of the new SIBS implant was inserted 2mm into the anterior chamber and the distal end placed in a subconjunctival space created by the surgeon. Biocompatibility of the device was studied by slit-lamp follow-up and intraocular pressure (IOP) measurements recorded periodically. Results: Biocompatibility of the MiDi was excellent. A low and diffuse bleb was observed with these devices. All SIBS tubes were patent 9 months after insertion. Immunostaining demonstrated non-continuous deposition of collagen with virtually no encapsulation. No macrophages or myofibroblast were visible around the SIBS polymer which was found more bioinert than the control PDMS. Conclusion: This newly designed glaucoma implant is clinically biocompatible in the rabbit model and maintained 100% patency at 9 months.

  7. Morphological Consequences of Frustration in ABC Triblock Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Radlauer, Madalyn R.; Sinturel, Christophe; Asai, Yusuke; Arora, Akash; Bates, Frank S.; Dorfman, Kevin D.; Hillmyer, Marc A. (UMM); (Nagoya); (Orleans)


    Three poly(styrene)-block-poly(isoprene)-block-poly(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core–shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

  8. Polymers with alternating anthracene and phenylene building blocks linked by ethynylene and/or vinylene units: Studying structure-properties-relationships

    Czech Academy of Sciences Publication Activity Database

    Boudiba, S.; Růžička, Aleš; Ulbricht, C.; Enengl, S.; Enengl, C.; Gasiorowski, J.; Yumusak, C.; Pokorná, Veronika; Výprachtický, Drahomír; Hingerl, K.; Zahn, D. R. T.; Tinti, F.; Camaioni, N.; Bouguessa, S.; Gouasmia, A.; Cimrová, Věra; Egbe, D. A. M.


    Roč. 55, č. 1 (2017), s. 129-143 ISSN 0887-624X R&D Projects: GA ČR(CZ) GA13-26542S Institutional support: RVO:61389013 Keywords : anthracene building block * charge transport * conjugated polymers Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.952, year: 2016

  9. Effects of surfactants on the properties of mortar containing styrene/methacrylate superplasticizer. (United States)

    Negim, El-Sayed; Kozhamzharova, Latipa; Khatib, Jamal; Bekbayeva, Lyazzat; Williams, Craig


    The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS) and either 1.5% polyvinyl alcohol (PVA) or 1.5% polyoxyethylene glycol monomethyl ether (POE). Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA), styrene/methyl methacrylate (St/MMA), and styrene/glycidyl methacrylate (St/GMA), in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

  10. Final Technical Report - Autothermal Styrene Manufacturing Process with Net Export of Energy

    Energy Technology Data Exchange (ETDEWEB)

    Trubac, Robert , E.; Lin, Feng; Ghosh, Ruma: Greene, Marvin


    The overall objectives of the project were to: (a) develop an economically competitive processing technology for styrene monomer (SM) that would reduce process energy requirements by a minimum 25% relative to those of conventional technology while achieving a minimum 10% ROI; and (b) advance the technology towards commercial readiness. This technology is referred to as OMT (Oxymethylation of Toluene). The unique energy savings feature of the OMT technology would be replacement of the conventional benzene and ethylene feedstocks with toluene, methane in natural gas and air or oxygen, the latter of which have much lower specific energy of production values. As an oxidative technology, OMT is a net energy exporter rather than a net energy consumer like the conventional ethylbenzene/styrene (EB/SM) process. OMT plants would ultimately reduce the cost of styrene monomer which in turn will decrease the costs of polystyrene making it perhaps more cost competitive with competing polymers such as polypropylene.

  11. Effects of Surfactants on the Properties of Mortar Containing Styrene/Methacrylate Superplasticizer (United States)

    Negim, El-Sayed; Kozhamzharova, Latipa; Khatib, Jamal; Bekbayeva, Lyazzat; Williams, Craig


    The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS) and either 1.5% polyvinyl alcohol (PVA) or 1.5% polyoxyethylene glycol monomethyl ether (POE). Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA), styrene/methyl methacrylate (St/MMA), and styrene/glycidyl methacrylate (St/GMA), in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA. PMID:24955426

  12. Effects of Surfactants on the Properties of Mortar Containing Styrene/Methacrylate Superplasticizer

    Directory of Open Access Journals (Sweden)

    El-Sayed Negim


    Full Text Available The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS and either 1.5% polyvinyl alcohol (PVA or 1.5% polyoxyethylene glycol monomethyl ether (POE. Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA, styrene/methyl methacrylate (St/MMA, and styrene/glycidyl methacrylate (St/GMA, in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

  13. Preparation of pH-sensitive amphiphilic block star polymers, their self-assembling characteristics and release behavior on encapsulated molecules

    KAUST Repository

    Song, Xiaowan


    Poly(ethylene glycol) (PEG), a polymer with excellent biocompatibility, was widely used to form nanoparticles for drug delivery applications. In this paper, based on PEG, a series of pH-sensitive amphiphilic block star polymers of poly(ethylene glycol)-block-poly(ethoxy ethyl glycidyl ether) (PEG-b-PEEGE) with different hydrophobic length were synthesized by living anionic ring-opening polymerization method. The products were characterized using 1H NMR and gel permeation chromatography. These copolymers could self-assemble in aqueous solution to form micellar structure with controlled morphologies. Transmission electron microscopy showed that the nanoparticles are spherical or rodlike with different hydrophilic mass fractions. The pH response of polymeric aggregates from PEG-b-PEEGE was detected by fluorescence probe technique at different pH. A pH-dependent release behavior was observed and pH-responsiveness of PEG-b-PEEGE was affected by the hydrophobic block length. These results demonstrated that star-shaped polymers (PEG-b-PEEGE) are attractive candidates as anticancer drug delivery carriers. © 2016 Springer-Verlag Berlin Heidelberg

  14. Preparation of acrylonitrile butadiene styrene fibers by pulse electrospinning

    Directory of Open Access Journals (Sweden)

    Dilyara Igimbayeva


    Full Text Available The paper represents the results on the preparation of polymer fibers of acrylonitrile butadiene styrene (ABS with the addition of iron as a modifying additives by pulse electrospinning. The virtue of the method of pulse electrospinning in comparison with classical electrospinning is to obtain fibers with a controlled length. To study the morphology of the fibers obtained samples were used the optical and scanning electron microscopy. To prove the presence of iron inside the fibers methods of elemental analysis and electron paramagnetic resonance were used. The technique and optimal conditions for obtaining fibers have been determined. The effect of technological parameters, concentrations of polymer solutions and modifying additives on the structure and morphology of the fibers were shown.

  15. Study of the mechanical properties of Acrylonitrile Butadiene Styrene - High Impact Polystyrene blends with Styrene Ethylene Butylene Styrene


    PEYDRO Miguel Angel; JUAREZ David; Sanchez-Caballero, Samuel; PARRES Francisco


    A binary blend Acrylonitrile Butadiene Styrene ¿ High Impact Polystyrene (ABS-HIPS 50% wt) was prepared on a twin-screw extruder at 190-210 oC. The different mechanical properties were then analyzed using tensile strength and impact tests. The analysis of mechanical properties showed a decrease in elongation at break and impact strength. On the other hand, we have prepared ternary blends of ABS-HIPS- Styrene Ethylene Butylene Styrene (SEBS), varying the percentage of SEBS from 10 to 30 %wt us...

  16. Study of the Influence of adding styrene-ethylene/butadiene-styrene in acrylonitrile-butadiene-styrene and polyethylene blends


    M.A. Peydro; F. Parres; Navarro Vidal, Raúl; Sanchez-Caballero, Samuel


    This work studies the recovery of two grades of acrylonitrile butadiene styrene (ABS) contaminated with low-density polyethylene (LDPE), by adding styrene ethylene/butadiene styrene (SEBS). To simulate contaminated ABS, virgin ABS was mixed with 1, 2, 4, and 8% of LDPE and then extruded at 220°C. After this, the ABS with the highest percentage of LDPE (8%) was mixed with 1, 2, 4, and 8% of SEBS and then extruded. Different blends were mechanically, rheologically, optically, and dimensionally ...

  17. Polymer modification of bitumen : Advances and challenges


    Zhu, Jiqing; Birgisson, Björn; Kringos, Niki


    Advances and challenges in the field of bitumen polymer modification for road construction during the last 40 years are reviewed in this paper. The history of bitumen polymer modification is described chronologically. Some popular plastomers and thermoplastic elastomers in bitumen modification are discussed regarding their advantages and disadvantages, including polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate (EVA), ethylene-butyl acrylate (EBA), styrene-butadiene-styrene (SBS),...

  18. Dielectric study of Poly(styrene- co -butadiene) Composites with Carbon Black, Silica, and Nanoclay

    KAUST Repository

    Vo, Loan T.


    Dielectric spectroscopy is used to measure polymer relaxation in styrene-butadiene rubber (SBR) composites. In addition to the bulk polymer relaxation, the SBR nanocomposites also exhibit a slower relaxation attributed to polymer relaxation at the polymer-nanoparticle interface. The glass transition temperature associated with the slower relaxation is used as a way to quantify the interaction strength between the polymer and the surface. Comparisons were made among composites containing nanoclay, silica, and carbon black. The interfacial relaxation glass transition temperature of SBR-clay nanocomposites is more than 80 °C higher than the SBR bulk glass transition temperature. An interfacial mode was also observed for SBR-silica nanocomposites, but the interfacial glass transition temperature of SBR-silica nanocomposite is somewhat lower than that of clay nanocomposites. An interfacial mode is also seen in the carbon black filled system, but the signal is too weak to analyze quantitatively. The interfacial polymer relaxation in SBR-clay nanocomposites is stronger compared to both SBR-carbon black and SBR-silica composites indicating a stronger interfacial interaction in the nanocomposites containing clay. These results are consistent with dynamic shear rheology and dynamic mechanical analysis measurements showing a more pronounced reinforcement for the clay nanocomposites. Comparisons were also made among clay nanocomposites using different SBRs of varying styrene concentration and architecture. The interfacial glass transition temperature of SBR-clay nanocomposites increases as the amount of styrene in SBR increases indicating that styrene interacts more strongly than butadiene with clay. © 2011 American Chemical Society.

  19. Molecular exchange in block copolymer micelles: when corona chains overlap (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung


    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  20. Examining the Self-Assembly of Rod-Coil Block Copolymers via Physics Based Polymer Models and Polarized X-Ray Scattering (United States)

    Hannon, Adam; Sunday, Daniel; Windover, Donald; Liman, Christopher; Bowen, Alec; Khaira, Gurdaman; de Pablo, Juan; Delongchamp, Dean; Kline, R. Joseph

    Photovoltaics, flexible electronics, and stimuli-responsive materials all require enhanced methodology to examine their nanoscale molecular orientation. The mechanical, electronic, optical, and transport properties of devices made from these materials are all a function of this orientation. The polymer chains in these materials are best modeled as semi-flexible to rigid rods. Characterizing the rigidity and molecular orientation of these polymers non-invasively is currently being pursued by using polarized resonant soft X-ray scattering (P-RSoXS). In this presentation, we show recent work on implementing such a characterization process using a rod-coil block copolymer system in the rigid-rod limit. We first demonstrate how we have used physics based models such as self-consistent field theory (SCFT) in non-polarized RSoXS work to fit scattering profiles for thin film coil-coil PS- b-PMMA block copolymer systems. We then show by using a wormlike chain partition function in the SCFT formulism to model the rigid-rod block, the methodology can be used there as well to extract the molecular orientation of the rod block from a simulated P-RSoXS experiment. The results from the work show the potential of the technique to extract thermodynamic and morphological sample information.

  1. In Situ Nitroxide-Mediated Polymerized Poly(acrylic acid as a Stabilizer/Compatibilizer Carbon Nanotube/Polymer Composites

    Directory of Open Access Journals (Sweden)

    Vitaliy Datsyuk


    the opportunity to reinitiate the polymerization of a second block that can be chosen among a wide range of monomers. This versatility is illustrated with a second block containing methyl acrylate (MA or styrene (S. Scanning and transmission electron microscopies confirm good CNT dispersion in the polymer network, while transmission electron microscopy also spots the anchorage locations of PAA on the CNT surface. Such nanotubes wrapped by diblock copolymers can be dispersed in various polymer matrices to create CNT—polymer composites. Conductivity measurements show that these composites obey a percolation-like power law with a low percolation threshold (less than 0.5 vol% and a high maximum conductivity (up to 1.5 S/cm at room temperature.

  2. Polymer flooding effect of seepage characteristics of the second tertiary combined model of L oilfield block B

    Directory of Open Access Journals (Sweden)

    Huan ZHAO


    Full Text Available The second tertiary combined model is applied to develop the second and third type reservoirs which have more oil layer quantity and strong anisotropism, compared to the regular main reservoir with polymer injection, whose seepage characteristics of polymer-injection-after-water-drive shows a remarkable difference, in addition. This development appears to have a larger effect on the remaining oil development and production. Simulating the second tertiary combined model by reservoir numerical simulation under different polymer molecular weight, polymer concentration, polymer injection rate on the polymer injection period, conclusions of the influenced seepage characteristics of original and added perforated interval pressure and water saturation are drawn. The conclusion shows that the polymer molecular weight could influence water saturation of added perforated interval; polymer concentration makes a significant impact on reservoir pressure; polymer injection rate has a great influence on the separate rate of original and added perforated interval. This research provides firm science evidence to the theory of the second tertiary combined model to develop and enhance oil injection-production rate.

  3. Influence of Poly(styrene-co-maleic acid) Copolymer Structure on the Properties and Self-Assembly of SMALP Nanodiscs. (United States)

    Hall, Stephen C L; Tognoloni, Cecilia; Price, Gareth J; Klumperman, Bert; Edler, Karen J; Dafforn, Tim R; Arnold, Thomas


    Polymer stabilized nanodiscs are self-assembled structures composed of a polymer belt that wraps around a segment of lipid bilayer, and as such are capable of encapsulating membrane proteins directly from the cell membrane. To date, most studies on these nanodiscs have used poly(styrene-co-maleic acid) (SMA) with the term SMA-lipid particles (SMALPs) coined to describe them. In this study, we have determined the physical and thermodynamic properties of such nanodiscs made with two different SMA copolymers. These include a widely used and commercially available statistical poly(styrene-co-maleic acid) copolymer (coSMA) and a reversible addition-fragmentation chain transfer synthesized copolymer with narrow molecular weight distribution and alternating styrene and maleic acid groups with a polystyrene tail, (altSMA). We define phase diagrams for each polymer, and show that, regardless of polymer topological structure, self-assembly is driven by the free energy change associated with the polymers. We also show that nanodisc size is polymer dependent, but can be modified by varying polymer concentration. The thermal stability of each nanodisc type is similar, and both can effectively solubilize proteins from the E. coli membrane. These data show the potential for the development of different SMA polymers with controllable properties to produce nanodiscs that can be optimized for specific applications and will enable more optimized and widespread use of the SMA-based nanodiscs in membrane protein research.

  4. Grafting of styrene onto fluoropolymers films

    Energy Technology Data Exchange (ETDEWEB)

    Geraldes, Adriana N.; Zen, Heloisa A.; Parra, Duclerc F.; Lugao, Ademar B.; Linardi, Marcelo [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente], E-mail:


    Grafting of styrene onto poly(vinylidenefluoride) (PVDF) and poly(tetrafluoroethylene) (PTFE) films was studied for the synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto PVDF and PTFE films was investigated by simultaneous method using a Co{sup 60} source. The films of PVDF and PTFE were irradiated at total dose of 20 to 120 kGy and chemical changes were monitored after contact with styrene. Films of PTFE and PVDF were immersed in styrene/toluene 1:1 and were submitted to gamma radiation. After irradiation the samples were evaluated at periods of 0, 7, 14, 21 and 28 days, at room temperature in order to measure the grafting degree. Results of infrared spectroscopic analysis (FTIR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and the degree of grafting (DOG) were evaluated. The characterization techniques showed that irradiated PVDF and PTFE films exhibited a much higher grafting degree at 120 kGy. (author)

  5. Aromatic Schiff Bases Multiply Substituted with Terminal Ethynyl Groups: Potential Building Blocks for Conjugated Polymers and Oligomers

    Czech Academy of Sciences Publication Activity Database

    Stahlová, S.; Sedláček, J.; Svoboda, J.; Polášek, Miroslav; Zednik, J.


    Roč. 68, č. 8 (2015), s. 1237-1248 ISSN 0004-9425 R&D Projects: GA ČR GAP108/12/1143 Grant - others:GA MŠk(CZ) LM2010005 Institutional support: RVO:61388955 Keywords : Aromatic compounds * Aromatic polymers * Conjugated polymers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.427, year: 2015

  6. ROMP- and RAFT-Based Guanidinium-Containing Polymers as Scaffolds for Protein Mimic Synthesis. (United States)

    Sarapas, Joel M; Backlund, Coralie M; deRonde, Brittany M; Minter, Lisa M; Tew, Gregory N


    Cell-penetrating peptides are an important class of molecules with promising applications in bioactive cargo delivery. A diverse series of guanidinium-containing polymeric cell-penetrating peptide mimics (CPPMs) with varying backbone chemistries was synthesized and assessed for delivery of both GFP and fluorescently tagged siRNA. Specifically, we examined CPPMs based on norbornene, methacrylate, and styrene backbones to determine how backbone structure impacted internalization of these two cargoes. Either charge content or degree of polymerization was held constant at 20, with diguanidinium norbornene molecules being polymerized to both 10 and 20 repeat units. Generally, homopolymer CPPMs delivered low amounts of siRNA into Jurkat T cells, with no apparent backbone dependence; however, by adding a short hydrophobic methyl methacrylate block to the guanidinium-rich methacrylate polymer, siRNA delivery to nearly the entire cell population was achieved. Protein internalization yielded similar results for most of the CPPMs, though the block polymer was unable to deliver proteins. In contrast, the styrene-based CPPM yielded the highest internalization for GFP (≈40 % of cells affected), showing that indeed backbone chemistry impacts protein delivery, specifically through the incorporation of an aromatic group. These results demonstrate that an understanding of how polymer structure affects cargo-dependent internalization is critical to designing new, more effective CPPMs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Writing on polymer chains. (United States)

    Lutz, Jean-François


    Synthetic polymer materials are currently limited by their inability to store information in their chains, unlike some well-characterized biopolymers. Nucleic acids store and transmit genetic information, and amino acids encode the complex tridimensional structures and functions within proteins. To confer similar properties on synthetic materials, researchers must develop"writing" mechanisms, facile chemical pathways that allow control over the primary structure of synthetic polymer chains. The most obvious way to control the primary structure is to connect monomer units one-by-one in a given order using iterative chemistry. Although such synthesis strategies are commonly used to produce peptides and nucleic acids, they produce limited yields and are much slower than natural polymerization mechanisms. An alternative strategy would be to use multiblock copolymers with blocks that have specified sequences. In this case, however, the basic storage element is not a single molecular unit, but a longer block composed of several repeating units. However, the synthesis of multiblock copolymers is long and tedious. Therefore, researchers will need to develop other strategies for writing information onto polymer chains. In this Account, I describe our recent progress in the development of sequence controlled polymerization methods. Although our research focuses on different strategies, we have emphasized sequence-regulation in chain-growth polymerization processes. Chain-growth polymerizations, particularly radical polymerization, are very convenient methods for synthesizing polymers. However, in most cases, such approaches do not lead to controlled monomer sequences. During the last five years, we have shown that controlled/living chain-growth polymerization mechanisms offer interesting advantages for sequence regulation. In such mechanisms, the chains form gradually over time, and therefore the primary structure can be tuned by using time-controlled monomer additions. For

  8. Silver(I 2,2'-(1,2-Phenylenedisulfanediyldiacetic Acid as a Molecular Building Block for a Silver(I-Cadmium(II Coordination Polymer

    Directory of Open Access Journals (Sweden)

    Ioana Georgeta Grosu


    Full Text Available Starting from heterotopic multidentate ligand 2,2'-(1,2-phenylenedisulfanediyldiacetic acid, (RS,RS,RS,RS/SS,SS,SS,SS-[Ag{1,2-C6H4(SCH2COOH2-κ2S,S'}2]BF4 (1 was prepared and further used as a building block for the synthesis of heterobimetallic Ag-Cd coordination polymer [Ag2Cd2{1,2-(OOCCH2S2C6H4}3 (H2O3·5H2O]n (2. Both complexes were characterized by X-ray structure analysis and conventional spectroscopic techniques.

  9. Electrically and chemically tunable soft-solid block copolymer structural color (Conference Presentation) (United States)

    Park, Cheolmin


    1D photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied due to their potential use in low-power reflective mode displays, e-books and sensors, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid swollen block copolymer films. Placement of a polymer/ionic liquid (IL) film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2vinyl pyridine) (PS-b-QP2VP) copolymer SC film allowed the development of R, G and B full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3V to +6V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

  10. Solvent and irradiation doses effects on the ion exchange capacity of sulfonated styrene grafted PVDF

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)


    Polymers exhibiting ion exchange capacity are studied for many years due to their application in several fields, such as membranes for proton exchange fuel cells, filtration membranes, heavy ions recovery and artificial muscles and sensors. Radiation induced grafting followed by sulfonation is a well-known way to obtain ion exchange polymers. Fluorinated polymers are frequently used as polymeric matrix for grafting due to their excellent physicochemical properties. Radiation induced grafting of styrene into poly (vinylidene fluoride) (PVDF) by simultaneous method in 1:1 styrene/toluene or styrene/N,N-dimethylformamide solutions was studied. Irradiations were performed under nitrogen atmosphere, room temperature and at doses of 5, 10 and 20 kGy with dose rate of 5 kGy.h{sup -1} from a {sup 60}Co gamma source. After washing, grafted materials were sulfonated in 10% chlorosulfonic acid/1,2-dichloroethane solutions for 4 h at room temperature. Characterization shows that increasing irradiation dose corresponds to increases in the grafting yield (GY %) gravimetrically calculated and these different solvents shows different grafting behaviors. Toluene allows no more than 3 % of grafting while DMF allows up to 55 % of grafting in the same condition. Grafting in toluene solution occurs on the surface and in DMF solution it occurs in the bulk, as confirmed by SEM. Both irradiation doses and solvent used have direct effects in the ion exchange capacities (calculated after titrations). FT-IR spectra exhibit new peaks after grafting and after sulfonation, attributed to grafted monomer and sulfonic groups attached to the styrene. DSC shows differences in thermal behavior of the polymer before and after each step. (author)

  11. High Solid Contents Copoly (Styrene/Butyl Acrylate)-Cloisite 30B Nanocomposites


    M. Mirzataheri


    Higher solid contents (20 % and 40 %) nanocomposites of poly (styrene-co-butyl acrylate) including higher content of Cloisite 30B (7 wt% and 10 wt %) were prepared via miniemulsion polymerization. Stability of the final latexes proved outstanding combination of polymerization procedure and surfactants. Morphological studies revealed by TEM, SAX and XRD showed three structures of core-shell, armored and individual dispersion of clay layers within the polymer particles. The effect of Cloisite 3...

  12. Highly conductive side chain block copolymer anion exchange membranes. (United States)

    Wang, Lizhu; Hickner, Michael A


    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  13. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika


    Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 1014 to 1.48 × 1015 pores/m 2 were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m-2 h-1 bar-1 and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes. © 2013 Elsevier Ltd. All rights reserved.

  14. Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    A. S. Almeida


    Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.

  15. Polymer Thin Film Stabilization. (United States)

    Costa, A. C.; Oslanec, R.; Composto, R. J.; Vlcek, P.


    We study the dewetting dynamics of thin polystyrene (PS) films deposited on silicon oxide surfaces using optical (OM) and atomic force (AFM) microscopes. Quantitative analysis of the hole diameter as a function of annealing time at 175^oC shows that blending poly(styrene-block-methyl-methacrylate) (PS-b-PMMA) with PS acts to dramatically slow down the dewetting rate and even stops holes growth before they impinge. AFM studies show that the hole floor is smooth for a pure PS film but contains residual polymer for the blend. At 5% vol., a PS-b-PMMA with high molar mass and low PMMA is a more effective stabilizing agent than a low molar mass/high PMMA additive. The optimum copolymer concentration is 3% vol. beyond which film stability doesn't improve. Although dewetting is slowed down relative to pure PS, PS/PS-b-PMMA bilayers dewet at a faster rate than blends having the same overall additive concentration.

  16. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan


    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin (ABS) and acrylonitrile–styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectivel...

  17. Inner Stucture of Thin Films of Lamellar Poly(styrene-b-butadiene) Diblock Copolymers as revealed by Grazing-Incidence Small-Angle Scattering

    DEFF Research Database (Denmark)

    Busch, Peter; Posselt, Dorthe; Smilgies, Detlef-Matthias


    The lamellar orientation in supported, thin films of poly(styrene-b-butadiene) (P(S-b-B)) depends on block copolymer molar mass. We have studied films from nine block copolymer samples with molar masses between 13.9 and 183 kg/mol using grazing-incidence small-angle X-ray scattering (GISAXS) and ...

  18. Fabrication of Bioactive Surfaces by Functionalization of Electroactive and Surface-Active Block Copolymers

    Directory of Open Access Journals (Sweden)

    Omotunde Olubi


    Full Text Available Biofunctional block copolymers are becoming increasingly attractive materials as active components in biosensors and other nanoscale electronic devices. We have described two different classes of block copolymers with biofuctional properties. Biofunctionality for block copolymers is achieved through functionalization with appropriate biospecific ligands. We have synthesized block copolymers of electroactive poly(3-decylthiophene and 2-hydroxyethyl methacrylate by atom transfer radical polymerization. The block copolymers were functionalized with the dinitrophenyl (DNP groups, which are capable of binding to Immunoglobulin E (IgE on cell surfaces. The block copolymers were shown to be redox active. Additionally, the triblock copolymer of α, ω-bi-biotin (poly(ethylene oxide-b-poly (styrene-b-poly(ethylene oxide was also synthesized to study their capacity to bind fluorescently tagged avidin. The surface-active property of the poly(ethylene oxide block improved the availability of the biotin functional groups on the polymer surfaces. Fluorescence microscopy observations confirm the specific binding of biotin with avidin.

  19. Molecular analysis on the utilization of oil palm empty fruit bunches fiber as reinforcement for acrylonitrile butadiene styrene biocomposites (United States)

    Hermawan, B.; Nikmatin, S.; Alatas, H.; Sudaryanto; Sukaryo, S. G.


    Oil palm empty fruit bunches (OPEFB) was one of the solid waste produced by the palm oil factory and were totally plentiful in biomass. OPEFB fiber used as reinforcement of polymer matrix acrylonitrile butadiene styrene (ABS). The use of FTIR is to see that there is no changes in the molecules of the constituent biocomposite ABS and OPEFB. The reactivity of butadiene and styrene through the double bond- π conjugated system, contributed to the bond reaction with the maleic acid as compatibilizer witch is grafted to the system. It is concluded that the posible grafting reaction occurs by the addition of the MAH to the double bond of the butadiene and styrene. The hydroxyl group of cellulose can interact with this maleic acid to form a bond through the carboxyl group.

  20. Thermotropic properties of phosphatidylcholine nanodiscs bounded by styrene-maleic acid copolymers. (United States)

    Dominguez Pardo, J J; Dörr, J M; Renne, M F; Ould-Braham, T; Koorengevel, M C; van Steenbergen, M J; Killian, J A


    Styrene-maleic acid copolymers (SMA) have been gaining interest in the field of membrane research due to their ability to solubilize membranes into nanodics. The SMA molecules act as an amphipathic belt that surrounds the nanodiscs, whereby the hydrophobic styrene moieties can insert in between the lipid acyl chains. Here we used SMA variants with different styrene-to-maleic acid ratio (i.e. 2:1, 3:1 and 4:1) to investigate how lipid packing in the nanodiscs is affected by the presence of the polymers and how it depends on polymer composition. This was done by analyzing the thermotropic properties of a series of saturated phosphatidylcholines in nanodiscs using laurdan fluorescence and differential scanning calorimetry. In all cases it was found that the temperature of the main phase transition (Tm) of the lipids in the nanodiscs is downshifted and that its cooperativity is strongly reduced as compared to the situation in vesicles. These effects were least pronounced for lipids in nanodiscs bounded by SMA 2:1. Unexpected trends were observed for the calorimetric enthalpy of the transition, suggesting that the polymer itself contributes, possibly by rearranging around the nanodiscs when the lipids adopt the fluid phase. Finally, distinct differences in morphology were observed for nanodiscs at relatively high polymer concentrations, depending on the SMA variant used. Overall, the results suggest that the extent of preservation of native thermodynamic properties of the lipids as well as the stability of the nanodiscs at high polymer concentrations is better for SMA 2:1 than for the other SMA variants. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  1. Fluorescent monomers as building blocks for dye labeled polymers: synthesis and application in energy conversion, biolabeling and sensors. (United States)

    Breul, Alexander M; Hager, Martin D; Schubert, Ulrich S


    This review focuses on side-chain functionalized polymers derived from direct (co)polymerization of fluorescent dyes. This overview about polymerizable dyes includes 1,8-naphthalimides, fluoresceins, rhodamines, coumarins, azo-dyes, oxadiazoles, diverse aromatic dyes as well as selected other dyes that cannot be classified within these groups. The discussed dyes have been functionalized with a polymerizable unit in order to apply straight-forward polymerization procedures. Therefore, the center of attention is set to the optical properties of the polymerizable dyes and the applicable polymerization techniques. Furthermore, the various applications (i.e., in biomedicine and pharmacy, as thermo-responsive materials and energy transfer materials, for dispersion of carbon nanotubes and others) of each polymer are discussed.

  2. Facile Synthesis of Multiblock Copolymers Containing Sequence-Controlled Peptides and Well-Defined Vinyl Polymers by Nitroxide-Mediated Polymerization. (United States)

    Nishimura, Shin-Nosuke; Higashi, Nobuyuki; Koga, Tomoyuki


    Precisely incorporating a wide range of structural and functional multiblocks along a polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein, a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well-defined vinyl polymers with a narrow polydispersity is reported. Cyclic oligopeptides have been developed that contain an alkoxyamine bond in the framework. By using this type of cyclic initiator, peptide-containing multiblock copolymers are successfully synthesized by nitroxide-mediated polymerization of styrene. To demonstrate the versatility of this method, radical (co)polymerizations were carried out for different monomers (p-chlorostyrene, 4-vinylpyridine, and styrene/acrylonitrile) and by three different cyclic peptide initiators with specific amino acid sequences. The resultant multiblock copolymer is foldable through intramolecular interactions between peptide blocks. It is believed that this approach will significantly advance the field of controlled polymer synthesis for complex structures and single-chain folding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Polystyrene cups and containers: styrene migration. (United States)

    Tawfik, M S; Huyghebaert, A


    The level of styrene migration from polystyrene cups was monitored in different food systems including: water, milk (0.5, 1.55 and 3.6% fat), cold beverages (apple juice, orange juice, carbonated water, cola, beer and chocolate drink), hot beverages (tea, coffee, chocolate and soup (0.0, 0.5, 1, 2, and 3.6% fat), take away foods (yogurt, jelly, pudding and ice-cream), as well as aqueous food simulants (3% acetic acid, 15, 50, and 100% ethanol) and olive oil. Styrene migration was found to be strongly dependent upon the fat content and storage temperature. Drinking water gave migration values considerably lower than all of the fatty foods. Ethanol at 15% showed a migration level equivalent to milk or soup containing 3.6% fat. Maximum observed migration for cold or hot beverages and take-away foods was 0.025% of the total styrene in the cup. Food simulants were responsible for higher migration (0.37% in 100% ethanol). A total of 60 food samples (yogurt, rice with milk, fromage, biogardes, and cheese) packed in polystyrene containers were collected from retail markets in Belgium, Germany, and the Netherlands. The level of styrene detected in the foods was always fat dependent.

  4. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Kapteijn, F.; Makkee, M.; Nederlof, C.

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  5. Graft Copolymerization and Characterization of Styrene with ...

    African Journals Online (AJOL)



    May 24, 2017 ... 1Department of Chemistry, Faculty of Science, Northwest University, P.M.B 3220, Kano, Nigeria. 2Department of Pure and ... In this study, styrene was successfully grafted onto chitosan by conventional free radical polymerization technique, using ..... radical species is very high, chain transfer and reaction ...

  6. The electrospinning of the copolymer of styrene and butyl acrylate for its application as oil absorbent. (United States)

    Xu, Naiku; Cao, Jipeng; Lu, Yuyao


    Electrospun polystyrene materials have been employed as oil absorbents, but they have visible drawbacks such as poor strength at low temperature and unreliable integrity because of brittleness and insufficient cohesive force among fibers. Butyl acrylate can polymerize into flexible chains, and its polymer can be used as elastomer and adhesive material. Thereby it is possible to obtain the material that has better performance in comparison with electrospun polystyrene material through the electrospinning of the copolymer of styrene and butyl acrylate. In this work, a polymer was synthesized through suspension polymerization by using styrene and butyl acrylate as comonomers. The synthesis of the copolymer of styrene and butyl acrylate was verified through dissolution and hydrolysis experimental data; as well through nuclear magnetic resonance spectrometry. The viscous flow activation energy of the solution consisting of copolymer and N, N-dimethylformamide was determined via viscosity method and then adopted to establish the entanglement characteristics of butyl acrylate's chain segments. Finally, in order to electrospin the copolymer solution into fibrous membrane, the effects of monomer feed ratio and spinning parameters were investigated. The prepared fibrous membrane was found to have a potential use as oil absorbent.

  7. Synthesis of Polymer Grafted Magnetite Nanoparticle with the Highest Grafting Density via Controlled Radical Polymerization (United States)

    Babu, Kothandapani; Dhamodharan, Raghavachari


    The surface-initiated ATRP of benzyl methacrylate, methyl methacrylate, and styrene from magnetite nanoparticle is investigated, without the use of sacrificial (free) initiator in solution. It is observed that the grafting density obtained is related to the polymerization kinetics, being higher for faster polymerizing monomer. The grafting density was found to be nearly 2 chains/nm2 for the rapidly polymerizing benzyl methacrylate. In contrast, for the less rapidly polymerizing styrene, the grafting density was found to be nearly 0.7 chain/nm2. It is hypothesized that this could be due to the relative rates of surface-initiated polymerization versus conformational mobility of polymer chains anchored by one end to the surface. An amphiphilic diblock polymer based on 2-hydroxylethyl methacrylate is synthesized from the polystyrene monolayer. The homopolymer and block copolymer grafted MNs form stable dispersions in various solvents. In order to evaluate molecular weight of the polymer that was grafted on to the surface of the nanoparticles, it was degrafted suitably and subjected to gel permeation chromatography analysis. Thermogravimetric analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to confirm the grafting reaction.

  8. Synthesis of Polymer Grafted Magnetite Nanoparticle with the Highest Grafting Density via Controlled Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Babu Kothandapani


    Full Text Available Abstract The surface-initiated ATRP of benzyl methacrylate, methyl methacrylate, and styrene from magnetite nanoparticle is investigated, without the use of sacrificial (free initiator in solution. It is observed that the grafting density obtained is related to the polymerization kinetics, being higher for faster polymerizing monomer. The grafting density was found to be nearly 2 chains/nm2for the rapidly polymerizing benzyl methacrylate. In contrast, for the less rapidly polymerizing styrene, the grafting density was found to be nearly 0.7 chain/nm2. It is hypothesized that this could be due to the relative rates of surface-initiated polymerization versus conformational mobility of polymer chains anchored by one end to the surface. An amphiphilic diblock polymer based on 2-hydroxylethyl methacrylate is synthesized from the polystyrene monolayer. The homopolymer and block copolymer grafted MNs form stable dispersions in various solvents. In order to evaluate molecular weight of the polymer that was grafted on to the surface of the nanoparticles, it was degrafted suitably and subjected to gel permeation chromatography analysis. Thermogravimetric analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to confirm the grafting reaction.

  9. Compatibilization of blends of low density polyethylene and poly(vinyl chloride) by segmented EB(SAN-block-EB)(n) block copolymers

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G

    Hydrogenated segmented poly[butadiene-block-((styrene-co-acrylonitrile)-block-butadiene)(n)] block copolymers, which were developed by use of the polymeric iniferter technique, were tested for their compatibilizing capacities for (10/90) LDPE/PVC blends. The acrylonitrile content of the SAN blocks

  10. Co-polymerization of methyl methacrylate and styrene via surfactant-free emulsion polymerization, as a potential material for photonic crystal application (United States)

    Kassim, Syara; Zahari, Siti Balqis; Tahrin, Rabiatul Addawiyah Azwa; Harun, Noor Aniza


    Photonic crystals are being the great interest of researcher to studies due to a variety of potential application for the interaction of light including the solar cells, optical sensors and paints. In order to evaluate the fabrication of photonic crystals thin film, a free-emulsifier emulsion copolymerization of styrene and methyl methacrylate was carried out. By using the self -assembly approach, this method offers the opportunity to produce crystalline polymer sphere in more ease operation, low cost and environmental friendly. The influences of the mixing ratio of monomer and amount of initiators were studied. In advance, the presence of styrene as co-monomer had improved the thermal degradation of polymer methyl methacrylate. While in changing the mixing ratio of styrene and methyl methacrylate resulted in particle size of the sphere. The size of polymer particles slightly increased on increasing volume of styrene monomer ratio. This occurred because the properties of styrene in water where it sparingly soluble and lead to coagulation of particles. This simple, yet effective method for preparing functional complex 3D structures has the potential to be used generically to fabricate a variety of functional porous 3D structures that could find application not only in new or improved photonic crystal (PC) devices but also in areas such as catalysis, solar cell, separation, fuel cells technology, microelectronics and optoelectronics.

  11. Hydrothermal Synthesis of Fe3O4 Nanoparticles and Flame Resistance Magnetic Poly styrene Nanocomposite

    Directory of Open Access Journals (Sweden)

    Kambiz Hedayati


    Full Text Available Fe3O4 nanostructures were synthesized via a facile hydrothermal reaction. The effect of various surfactants such as cationic and anionic on the morphology of the product was investigated. Magnetic nanoparticles were added to poly styrene for preparation of magnetic nanocomposite. Nanostructures were then characterized using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The magnetic properties of the samples were also investigated using vibrating sample magnetometer. The magnesium ferrite nanoparticles exhibit super paramagnetic behaviour at room temperature, with a saturation magnetization of 66 emu/g and a coercivity less than 5 Oe. Distribution of the magnetic nanoparticles into poly styrene matrix increases the coercivity. Nanoparticles appropriately enhanced flame retardant property of the PS matrix. Nanoparticles act as barriers which decrease thermal transport and volatilization during decomposition of the polymer.

  12. Matrix-assisted laser desorption/ionization-collision induced dissociation of poly(styrene). (United States)

    Jackson, A T; Yates, H T; Scrivens, J H; Green, M R; Bateman, R H


    Matrix-assisted laser desorption/ionization-collision induced dissociation (MALDI-CID) has been employed for the analysis of poly(styrene) in a tandem hybrid sector-time of flight instrument. Spectra are shown for adducts of poly(styrene) with copper and silver ions. The distributions of fragment ion peaks were found to be consistent from precursor ions containing both metal ions. It is shown how the masses of the end groups of the polymer may be inferred from the mass-to-charge ratios of two of the series of ion peaks that are seen in the MALDI-CID spectra. Mechanisms are proposed for the formation of some of the other series of ion peaks that are observed in the spectra.

  13. Polymer Coatings of Cochlear Implant Electrode Surface - An Option for Improving Electrode-Nerve-Interface by Blocking Fibroblast Overgrowth.

    Directory of Open Access Journals (Sweden)

    C Hadler

    Full Text Available Overgrowth of connective tissue and scar formation induced by the electrode array insertion increase the impedance and, thus, diminish the interactions between neural probes as like cochlear implants (CI and the target tissue. Therefore, it is of great clinical interest to modify the carrier material of the electrodes to improve the electrode nerve interface for selective cell adhesion. On one side connective tissue growth needs to be reduced to avoid electrode array encapsulation, on the other side the carrier material should not compromise the interaction with neuronal cells. The present in vitro-study qualitatively and quantitatively characterises the interaction of fibroblasts, glial cells and spiral ganglion neurons (SGN with ultrathin poly(N,N-dimethylacrylamide (PDMAA, poly(2-ethyloxazoline (PEtOx and poly([2-methacryloyloxyethyl]trimethylammoniumchlorid (PMTA films immobilised onto glass surfaces using a photoreactive anchor layer. The layer thickness and hydrophilicity of the polymer films were characterised by ellipsometric and water contact angle measurement. Moreover the topography of the surfaces was investigated using atomic force microscopy (AFM. The neuronal and non-neuronal cells were dissociated from spiral ganglions of postnatal rats and cultivated for 48 h on top of the polymer coatings. Immunocytochemical staining of neuronal and intermediary filaments revealed that glial cells predominantly attached on PMTA films, but not on PDMAA and PEtOx monolayers. Hereby, strong survival rates and neurite outgrowth were only found on PMTA, whereas PDMAA and PEtOx coatings significantly reduced the SG neuron survival and neuritogenesis. As also shown by scanning electron microscopy (SEM SGN strongly survived and retained their differentiated phenotype only on PMTA. In conclusion, survival and neuritogenesis of SGN may be associated with the extent of the glial cell growth. Since PMTA was the only of the polar polymers used in this study

  14. Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays (United States)

    Loewe, Robert S.; Tomizaki, Kin-ya; Lindsey, Jonathan S.


    The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: wherein m is at least 1; X.sup.1 is a charge separation group, and X.sup.2 through X.sup.m+1 are chromophores. At least one of X.sup.2 through X.sup.m+1 has at least one perylene group coupled thereto.

  15. Synthesis of Hydrophilic and Amphiphilic Acryl Sucrose Monomers and Their Copolymerisation with Styrene, Methylmethacrylate and α- and β-Pinenes

    Directory of Open Access Journals (Sweden)

    Maria Teresa Barros


    Full Text Available Herein, we report the synthesis of monomethacryloyl sucrose esters, and their successful free radical homo- and co-polymerisation with styrene, methylmethacrylate, α- and β-pinene. The chemical, physical, structural and surface chemical properties of these polymers, containing a hydrophobic olefin backbone and hydrophilic sugar moieties as side chains, have been investigated. Biodegradation tests of the copolymer samples by a microbial fungal culture (Aspergillus niger method showed good biodegradability. The chemical structure and surface chemistry of the synthesized homo- and co-polymers demonstrate their potential technological relevance as amphiphilic and biodegradable polymers.

  16. Study of the thermal properties of Acrylonitrile Butadiene Styrene - High Impact Polystyrene blends with Styrene Ethylene Butylene Styrene


    PEYDRO Miguel Angel; JUAREZ David; Sanchez-Caballero, Samuel; PARRES Francisco


    A binary blend Acrylonitrile Butadiene Styrene ¿ High Impact Polystyrene (ABS-HIPS 50% wt) was prepared on a twin-screw extruder at 190-210 oC. The different properties were then analyzed using melt flow index (MFI), thermogravimetric analysis (TGA), and Fourier Transform Infrared spectroscopy (FTIR). FTIR analysis indicated heterogeneous distribution of the blend in injected pieces and SEM micrographs show heterogeneous distribution of both phase (ABS and HIPS). On the other hand, we have pr...

  17. Hydroxyethyl cellulose doped with copper(II) phthalocyanine-tetrasulfonic acid tetrasodium salt as an effective dual functional hole-blocking layer for polymer light-emitting diodes (United States)

    Wu, Cheng-Liang; Chen, Yun


    We report a doping method to improve the performance of solution-processed polymer light-emitting diodes (PLEDs). Doping 12 wt% copper(II) phthalocyanine-tetrasulfonated acid tetrasodium salt (TS-CuPc) into hydroxyethyl cellulose (HEC) as a dual functional hole-blocking layer (df-HBL) of multilayer PLED (glass/ITO/PEDOT:PSS/HY-PPV/TS-CuPc-doped HEC/LiF/Al) significantly enhanced maximum luminance, maximum current and power efficiency over that without the df-HBL (10,319 cd/m2, 2.98 cd/A and 1.24 lm/W) to (29,205 cd/m2, 13.27 cd/A and 9.56 lm/W). CV measurements reveal that HEC possesses a powerful hole-blocking capability. Topography and conductivity AFM images show that doping TS-CuPc increases the interfacial contact area and interfacial conductivity, which can overcome the insulating nature of HEC and thus further facilitate electron injection. Enhancements in device performance are attributed to the improved carrier balance and recombination in the presence of df-HBL, confirmed in electron-only and hole-only devices. Moreover, apparently raised open-circuit voltages provide further evidence that enhanced electron injection is indeed realized by the df-HBL. This study demonstrates an effective approach to develop highly efficient PLEDs.

  18. Improved synthesis of polystyrene-poly(ethylene oxide)-heparin block copolymers

    NARCIS (Netherlands)

    Vulic, I.; Loman, A.J.B.; Feijen, Jan; Okano, T.; Kim, S.W.


    A novel procedure for the synthesis of block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic block of poly(ethylene oxide) and a bioactive block of nitrous acid-degraded heparin was developed. Amino-semitelechelic polystyrene was prepared by anionic polymerization of styrene

  19. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen


    , by NaOH catalyzed deprotection, the 4-acetoxystyrene polymers including triblock copolymer poly(4-acetoxystyrene-b-isobutylene-b-4-toxystyrene) suffered from some degrees of coupling or even gelation, except for poly(styrene-b-4-acetoxystyrene-b-styrene) which also by this method could be conveniently...


    Directory of Open Access Journals (Sweden)

    A. A. Sedykh


    Full Text Available Summary. In the prevention of gastric diseases flexible optical fiber harness with camera and lighting after its extraction from the stomach is subjected to disassembly and continuous sterilization. Protection flexible optical fiber tourniquet, disposable and transparent sheath reduces the duration of the disassembly and sterilization. As the material for the shell of the recommended developed by the Voronezh branch of the FSUE "NIISK" high-styrene block copolymers Styrotep-65. The aim of this work was the development of technologies for films, protective shells of TEC and estimation of their technical parameters. As a benchmark comparison was tested extruded film Styrotep-65. The orientation of the macromolecules of the polymer along the sleeve during extraction provided the anisotropy of the properties of the film along and across the sleeves. In the study of properties of solutions of thermoplastic elastomer is established that the increase in solution viscosity provides greater film thickness in a single dunking them in forms. We investigated the effect of the concentration of a solution Styrotep-65 in toluene and the speed of rotation of a spindle of a Brookfield viscometer PV-E on their viscosity. With increasing concentration of the polymer solution with 19,0 to 26.8 % of the mass. the level of viscosity was increased from 104 to 330 MPa•S. In the interval of increasing the rotational speed of the spindle from 2.0 to 10.0 rpm viscosity solutions is not dependent on the concentration increased due to manifestations of thixotropy. A further increase in the speed of rotation of the spindle 10 to 100 rpm did not affect the viscosity of the solutions. This is true for ideal fluids. Film cast on a horizontal surface of the cellophane from a 10 % toluene solution, was characterized by lower strength than extruded, but with a large elongation at break. Determined the impact of the multiplicity of dipping forms in solution and polymer solution

  1. High Triplet Energy Level Achieved by Tuning the Arrangement of Building Blocks in Phosphorescent Polymer Backbones for Furnishing High Electroluminescent Performances in Both Blue and White Organic Light-Emitting Devices. (United States)

    Liu, Boao; Dang, Feifan; Tian, Zhuanzhuan; Feng, Zhao; Jin, Deyuan; Dang, Wanping; Yang, Xiaolong; Zhou, Guijiang; Wu, Zhaoxin


    A high triplet energy level (E T ) of ca. 2.83 eV has been achieved in a novel polymer backbone through tuning the arrangement of two kinds of building blocks, showing enhanced hole injection/transporting capacity. Based on this new polymer backbone with high E T , both blue and white phosphorescent polymers were successfully developed with a trade-off between high E T and enhanced charge-carrier transporting ability. In addition, their photophysical features, electrochemical behaviors, and electroluminescent (EL) properties have been characterized in detail. Benefitting from the advantages associated with the novel polymer backbone, the blue phosphorescent polymers show top-ranking EL performances with a maximum luminance efficiency (η L ) of 15.22 cd A -1 , corresponding to a power efficiency (η P ) of 12.64 lm W -1 , and external quantum efficiency (η ext ) of 6.22% and the stable Commission Internationale de L'Eclairage (CIE) coordinates of (0.19, 0.38). Furthermore, blue-orange (B-O) complementary-colored white phosphorescent polymers based on this novel polymer backbone were also obtained showing encouraging EL efficiencies of 12.34 cd A -1 , 9.59 lm W -1 , and 4.10% in the optimized WOLED together with exceptionally stable CIE coordinates of (Δx = 0.014, Δy = 0.010) in a wide driving voltage range from 4 to 16 V. All of these attractive EL results achieved by these novel phosphorescent polymers show the great potential of this new polymer backbone in developing highly efficient phosphorescent polymers.

  2. Functionalized 1,2,3-triazoles as building blocks for photoluminescent POLOs (polymers of oligomers) of copper(I). (United States)

    Bai, Shi-Qiang; Kwang, Jia Yi; Koh, Lip Lin; Young, David J; Hor, T S Andy


    Two 3-D and one 2-D metal-organic frameworks [Cu(8)I(8)(L1)(4)](n) (1), [Cu(8)I(8)(L2)(4)](n) (2) and [Cu(4)I(4)(L3)(2)](n) ()3 were synthesized using three novel pyridine and pyrazole supported 1,2,3-triazoles, 1-(4-picolyl)-4-butyl-1H-1,2,3-triazole (L1), 1-(4-picolyl)-4-pentyl-1H-1,2,3-triazole (L2) and 1-(4-picolyl)-4-(3,5-dimethylpyrazolylmethyl)-1H-1,2,3-triazole (L3). In both complexes 1 and 2, there co-exist a 1-D Cu(I) oligomer and Cu(4) tetrahedron cluster in the 3-D polymeric structures. Complex 3 shows a 2-D (4, 4) net with the stair-step Cu(4)I(4) as node and L3 as a building block. All three complexes exhibit photoluminescence.

  3. Marginal discrepancy dimensions of single unit metal crowns fabricated by using CAD-CAM-milled acrylate resin polymer blocks or a conventional waxing technique. (United States)

    Lalande, David; Hodd, Jeffrey A; Brousseau, John S; Ramos, Van; Dunham, Daniel; Rueggeberg, Frederick


    Because crowns with open margins are a well-known problem and can lead to complications, it is important to assess the accuracy of margins resulting from the use of a new technique. Currently, data regarding the marginal fit of computer-aided design and computer-aided manufacturing (CAD-CAM) technology to fabricate a complete gold crown (CGC) from a castable acrylate resin polymer block are lacking. The purpose of this in vitro study was to compare marginal discrepancy widths of CGCs fabricated by using either conventional hand waxing or acrylate resin polymer blocks generated by using CAD-CAM technology. A plastic model of a first mandibular molar was prepared by using a 1-mm, rounded chamfer margin on the entire circumference of the tooth. The master die was duplicated 30 times, and 15 wax patterns were fabricated by using a manual waxing technique, and 15 were fabricated by using CAD-CAM technology. All patterns were invested and cast, and resulting CGCs were cemented on their respective die by using resin-modified glass ionomer cement. The specimens were then embedded in acrylic resin and sectioned buccolingually. The buccal and lingual marginal discrepancies of each sectioned portion were measured by using microscopy at ×50 magnification. Data were subjected to repeated measures 2-way ANOVA, by using the Tukey post hoc pairwise comparison test (α=.05). The factor of "technique" had no significant influence on marginal discrepancy measurement (P=.431), but a significant effect of "margin location" (P=.019) was noted. The confounding combination of factors was found to be significantly lower marginal discrepancy dimensions of the lingual margin discrepancy than on the buccal side by using CAD-CAM technology. The marginal discrepancy of CAD-CAM acrylate resin crowns was not significantly different from those made with a conventional manual method; however, lingual margin discrepancies present from CAD-CAM-prepared crowns were significantly less than those

  4. Effect of annealing and UV-radiation time over micropore architecture of self-assembled block copolymer thin film

    Directory of Open Access Journals (Sweden)

    G. del C. Pizarro


    Full Text Available Block copolymers have been recognized as versatile materials to prepare nanoporous polymer films or membranes, but their potential has not been completely explored. This study focuses on the formation and characterization of nanoporous polymer films based on poly(styrene-block-(methylmethacrylate/methacrylic acid; (PS-b-MMA/MAA were obtained through atom transfer radical polymerization (ATRP, by using two different protocols: annealing and annealingirradiation; for improving the formation of microporous surface. The composition, crystallinity and structural order of the films were studied by Raman spectroscopy. The film polymer thickness was obtained through very high resolution ellipsometry (VHRE. Finally, atomic force microcopy (AFM and scanning electron microscopy (SEM techniques were used to detect changes in the porous-structure. These results show that the morphological properties of the block copolymer were affected via the modification of two variables, UV-radiation time and annealing. SEM and AFM micrographs showed that the morphology exhibit a porous ordered structure. Contact angle measurement suggests additional interactions between hydrophilic functional groups that influence the film wettability.

  5. High Solid Contents Copoly (Styrene/Butyl Acrylate-Cloisite 30B Nanocomposites

    Directory of Open Access Journals (Sweden)

    M. Mirzataheri


    Full Text Available Higher solid contents (20 % and 40 % nanocomposites of poly (styrene-co-butyl acrylate including higher content of Cloisite 30B (7 wt% and 10 wt % were prepared via miniemulsion polymerization. Stability of the final latexes proved outstanding combination of polymerization procedure and surfactants. Morphological studies revealed by TEM, SAX and XRD showed three structures of core-shell, armored and individual dispersion of clay layers within the polymer particles. The effect of Cloisite 30B content on the barrier properties presents excellent and wide use of these films for packaging and nanocoatings industries.

  6. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (Postprint)

    National Research Council Canada - National Science Library

    Drazowski, Daniel B; Lee, Andre; Haddad, Timothy S


    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

  7. Reduced hydrophobic interaction of polystyrene surfaces by spontaneous segregation of block copolymers with oligo (ethylene glycol) methyl ether methacrylate blocks: force measurements in water using atomic force microscope with hydrophobic probes. (United States)

    Zhang, Rui; Seki, Akiko; Ishizone, Takashi; Yokoyama, Hideaki


    Reduction of hydrophobic interaction in water is important in biological interfaces. In our previous work, we have found that poly(styrene- b-triethylene glycol methyl ether methacrylate) (PS-PME3MA) segregates the PME3MA block to the surface in hydrophobic environment, such as in air or in a vacuum, and shows remarkable resistance against adsorption or adhesion of proteins, platelets, and cells in water. In this paper, we report that atomic force microscopy (AFM) with hydrophobic probes can directly monitor the reduced hydrophobic interaction of the PS surfaces modified by poly(styrene- b-origoethylene glycol methyl ether methacrylate) (PS-PME NMA), where N is the number of ethylene glycol units. The pull-off forces between the hydrophobic probes that are coated with octyltrichlorosilane (OLTS) and the PS-PME NMA modified polystyrene (PS) surfaces in water were measured. The absolute spring constants and tip-curvatures of the AFM cantilevers were measured to compute the work of adhesion by the Johnson, Kendall, and Roberts (JKR) theory, which relates the pull-off force at which the separation occurs between a hemisphere and a plane to the work of adhesion. The hydrophobic interactions between the hydrophobic tip and polymer surfaces in water were greatly reduced with the segregated PME NMA blocks. The hydrophobic interactions decrease with increasing N of the series of PS-PME NMA and show a correlation with the amount of protein adsorbed.

  8. Styrene exposure during the manufacturing of reinforced fiberglass pipe

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, K.E.


    Considering the large number of employees exposed to airborne styrene during the manufacturing of reinforced fiberglass pipe and the absence of appropriate information to define airborne styrene exposure and the resulting levels of urinary mandelic acid, it was necessary that these parameters be evaluated in an actual industrial setting in order to appropriately monitor and control health hazards in the work place. Styrene measurements were collected at eight work stations over a 5-year period at the world's largest manufacturer of styrenated reinforced fiberglass pipe. Pre- and post-shift urinary mandelic acid was measured for 16 employees for 3-consecutive days. The data obtained were statistically analyzed to determine the mean styrene exposure at each work station and the relationship between airborne styrene and pre-and post-shift urinary mandelic acid. The results of this study indicated that both the pre- and post-shift urinary mandelic acid measurements can be utilized to confirm human exposure to styrene. Post-shift measurements are more reflective of daily variations in styrene exposure, whereas pre-shift urinary mandelic acid was found to correlate best to the long-term airborne styrene concentrations (r = 0.787). The prediction equations of NIOSH and ACGIH for the arithmetic mean airborne styrene concentration from post-shift mandelic acid were not valid for the low levels of styrene exposure and urinary mandelic acid concentrations found in this study. Significant changes in the post-shift to pre-shift urinary mandelic acid concentrations were observed.

  9. Near-infrared light stimuli-responsive synergistic therapy nanoplatforms based on the coordination of tellurium-containing block polymer and cisplatin for cancer treatment. (United States)

    Li, Feng; Li, Tianyu; Cao, Wei; Wang, Lu; Xu, Huaping


    Cisplatin (CDDP) has received worldwide approval for clinical use in the past decades. However, its development in cancer chemotherapy was overshadowed by severe side effects and drug resistance. Herein, we developed a CDDP drug delivery system with high encapsulation efficiency and near-infrared light stimuli-responsive drug release properties based on the coordination of novel tellurium-containing block polymer (PEG-PUTe-PEG) and CDDP. The nanocarriers made from PEG-PUTe-PEG were loaded with CDDP and indocyanine green (ICG) simultaneously. The coordination chemistry between CDDP and tellurium guaranteed the nanocarrier a high stability in plasma and prolonged circulation time in vivo by reducing possible penetration of water molecule into the nanoparticles. Under the stimuli of a near-infrared laser, an amount of ROS can be generated by irradiation of ICG. The tellurium is easily oxidized by ROS because of the low electronegativity of tellurium. The CDDP could be rapidly released from the nanocarriers along with the oxidation of the tellurium at the tumor sites as the oxidized tellurium will weaken the coordination interaction with CDDP. In addition, the encapsulated ICG played a synergistic antitumor effect through photothermal effect with mild laser irradiation. The integrated strategy achieved higher antitumor efficacy and showed minimal side effects compared with the CDDP alone. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Patchy polymer colloids with tunable anisotropy dimensions. (United States)

    Kraft, Daniela J; Hilhorst, Jan; Heinen, Maria A P; Hoogenraad, Mathijs J; Luigjes, Bob; Kegel, Willem K


    We present the synthesis of polymer colloids with continuously tunable anisotropy dimensions: patchiness, roughness, and branching. Our method makes use of controlled fusion of multiple protrusions on highly cross-linked polymer particles produced by seeded emulsion polymerization. Carefully changing the synthesis conditions, we can tune the number of protrusions, or branching, of the obtained particles from spheres with one to three patches to raspberry-like particles with multiple protrusions. In addition to that, roughness is generated on the seed particles by adsorption of secondary nucleated particles during synthesis. The size of the roughness relative to the smooth patches can be continuously tuned by the initiator, surfactant, and styrene concentrations. Seed colloids chemically different from the protrusions induce patches of different chemical nature. The underlying generality of the synthesis procedure allows for application to a variety of seed particle sizes and materials. We demonstrate the use of differently sized polyNIPAM (poly-N-isopropylacrylamide), as well as polystyrene and magnetite filled polyNIPAM seed particles, the latter giving rise to magnetically anisotropic colloids. The high yield together with the uniform, anisotropic shape make them interesting candidates for use as smart building blocks in self-assembling systems.

  11. Controlled Release of Imidacloprid from Poly Styrene-Diacetone - Nanoformulation (United States)

    Qian, Kun; Guo, Yanzhen; He, Lin


    Imidacloprid is a neonicotinoids insecticide, which is important for the cash crops such as tomato, rape and so on. The conventional formulation does not only increase the loss of pesticide but also leads to environmental pollution. Controlled-release formulations of pesticide are highly desirable not only for attaining the most effective utilization of the pesticide, but also for reducing environmental pollution. Pesticide imidacloprid was incorporated in poly (styrene-diacetone crylamide)-based formulation to obtain controlled release properties, and the imidacloprid nanocontrolled release formulation was characterized by infrared (IR) and field emission scanning electron microscope (FESEM). Factors related to loading efficiency, swelling and release behaviors of the formulation were investigated. It showed that the loading efficiency could reach about 40% (w/w). The values for the diffusion exponent "n" were in the range of 0.31-0.58, which indicated that the release of imidacloprid was diffusion-controlled. The time taken for 50% of the active ingredient to be released into water, T50, was also calculated for the comparison of formulations in different conditions. The results showed that the formulation with higher temperature and more diacetone crylamide had lower value of T50, which means a quicker release of the active ingredient. This study highlighted some pieces of evidence that improved pesticide incorporation and slower release were linked to potential interactions between the pesticide and the polymer.

  12. Matrix-assisted laser desorption/ionization sample preparation optimization for structural characterization of poly(styrene-co-pentafluorostyrene) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Tisdale, Evgenia; Kennedy, Devin; Wilkins, Charles, E-mail:


    Graphical abstract: -- Highlights: •We optimized sample preparation for MALDI TOF poly(styrene-copentafluorostyrene) co-polymers. •Influence of matrix choice was investigated. •Influence of matrix/analyte ratio was examined. •Influence of analyte/salt ratio (for Ag+ salt) was studied. -- Abstract: The influence of the sample preparation parameters (the choice of the matrix, matrix:analyte ratio, salt:analyte ratio) was investigated and optimal conditions were established for the MALDI time-of-flight mass spectrometry analysis of the poly(styrene-co-pentafluorostyrene) copolymers. These were synthesized by atom transfer radical polymerization. Use of 2,5-dihydroxybenzoic acid as matrix resulted in spectra with consistently high ion yields for all matrix:analyte:salt ratios tested. The optimized MALDI procedure was successfully applied to the characterization of three copolymers obtained by varying the conditions of polymerization reaction. It was possible to establish the nature of the end groups, calculate molecular weight distributions, and determine the individual length distributions for styrene and pentafluorostyrene monomers, contained in the resulting copolymers. Based on the data obtained, it was concluded that individual styrene chain length distributions are more sensitive to the change in the composition of the catalyst (the addition of small amount of CuBr{sub 2}) than is the pentafluorostyrene component distribution.

  13. Otoacoustic emission sensitivity to exposure to styrene and noise. (United States)

    Sisto, R; Cerini, L; Gatto, M P; Gherardi, M; Gordiani, A; Sanjust, F; Paci, E; Tranfo, G; Moleti, A


    The ototoxic effect of the exposure to styrene is evaluated, also in the presence of simultaneous exposure to noise, using otoacoustic emissions as biomarkers of mild cochlear damage. Transient-evoked and distortion product otoacoustic emissions were recorded and analyzed in a sample of workers (15 subjects) exposed to styrene and noise in a fiberglass manufacturing facility and in a control group of 13 non-exposed subjects. Individual exposure monitoring of the airborne styrene concentrations was performed, as well as biological monitoring, based on the urinary concentration of two styrene metabolites, the Mandelic and Phenylglyoxylic acids. Noise exposure was evaluated using wearable phonometers, and hearing loss with pure tone audiometry. Due to their different job tasks, one group of workers was exposed to high noise and low styrene levels, another group to higher styrene levels, close to the limit of 20 ppm, and to low noise levels. A significant negative correlation was found between the otoacoustic emission levels and the concentration of the styrene urinary metabolites. Otoacoustic emissions, and particularly distortion products, were able to discriminate the exposed workers from the controls, providing also a rough estimate of the slope of the dose-response relation between otoacoustic levels and styrene exposure.

  14. Synthesis and antibacterial activities of cyclodimers of styrene oxides

    African Journals Online (AJOL)

    A simple synthetic procedure for preparation of 1,4-dioxanes or 1,3-dioxolanes from styrene oxides is described. Electron-donating groups on the aromatic ring of the styrene oxides were found to favour formation of 1,4-dioxanes while electron-withdrawing groups favoured formation of 1,3-dioxolanes. Antibacterial activities ...

  15. Application of Lignin as Antioxidant in Styrene Butadiene Rubber Composite (United States)

    Liu, Shusheng; Cheng, Xiansu


    Lignin isolated from enzymatic hydrolyzed cornstalks (EHL) is a renewable natural polymer, and rubber is one of the most important polymer materials. The application of EHL in rubber industry is of great significance. The influence of EHL and antioxidant RD on the vulcanizing characteristics, thermal oxidative aging stability under free condition, and water extraction resistance of styrene-butadiene rubber (SBR) were investigated. The effect of EHL/antioxidant D composite antioxidant on the thermal oxidative ageing of SBR was also evaluated. Results showed that the protection of SBR from thermal oxidative aging by EHL/antioxidant D composite antioxidant was superior to that of antioxidant D. This is because EHL molecules have hindered phenol group and have excellent auxiliary antioxidant role with antioxidant D. Moreover, the influence of EHL on the vulcanizing characteristics of SBR compounds was better than that of antioxidant RD, and EHL can reduce the cure rate and increase the optimum cure time. It is because that the EHL molecules have hindered phenol group and methoxy group, which can form a special structure to capture free radical and terminate the chain reaction. The retained tensile strength of SBR compounds with EHL was similar to that of the samples with antioxidant RD, while the retained elongation at break of SBR compounds with EHL was higher than that of the samples with antioxidant RD. In addition, the SBR compounds with EHL have a good water extraction resistance property, which was similar to the samples with antioxidant RD. This is because EHL have large molecular weight, good stability and low solubility in water. In conclusion, due to the low price, abundant resources, non-toxic and pollution-free, etc., EHL will have broad application prospect.


    Directory of Open Access Journals (Sweden)

    Mr Wiendartun


    Full Text Available Hydrophilic properties of organic polymer such as Poly (2-Vinylpyridine- Co-Styrene have been found to have a correlation with other physical properties especially the electric resistivity. In this work, we have studied one of the physical properties of a polymer material, Poly (2-Vinylpyridine- Co-Styrene, that is the electric resistivity. It was studied on the basis of its relation with the concentration, temperature, humidity and the distance between their electrodes. The sample fabricated consists of two types of consentration: 0.03 gr/ml and 0.05 gr/ml with the distance between the two electrodes are 0.40 mm and 0.80 mm respectively. Towards these samples, we investigated the resistance coefficient for every 2% change in humidity for both drying and watering processes. From the experiment we obtain the following results: 1 There is hysteresis during the watering and drying processes indicating the continuity of resistance of this material, 2 Sample with smaller distance of electrodes performs better than that of the longer ones, 3 Sample fabricated from solution with higher concentration performs better than that of the lower ones, 4 Room temperature plays a significant role on the performance of the polymer material between the associated electrodes. These results could be used as a stepping-stone toward the more advance research leading the determination of film stability, resistancy upon temperature variation etc, so that this polymer material could be further developed into the humidity sensor device material. Key words: Hydrophilic, electric resistance, humidity sensor and polymer.

  17. Nanopatterned block copolymers for use as vascular biomaterials (United States)

    Silverstein, Joshua S.

    Manipulation of surface topography or chemistry has been a growing trend in efforts to enhance the properties of medical devices. Understanding the interactions of biomolecules with nanoengineered surfaces is vital to assess the safety and efficacy of devices that incorporate these structures. In this dissertation, a model block copolymer (BCP) system based on poly(styrene)-block-poly(1,2-butadiene) was systematically modified using photochemical thiol-ene chemistry. Poly(1,2-butadiene) molecular weight and thiol-ene ratios were systematically varied based on a model monomer, boc-cysteamine, to determine the efficiency of the reaction. The results demonstrate the polydispersity index of modified BCPs significantly increased when low thiol-ene ratios were employed and sometimes induced gelation of the reacted polymers. Using a tenfold excess of thiol, functionalizations between 60-90% were obtained for an acid, amine, amide, and a pharmaceutical with a pendant thiol. Calorimetry showed a 30-60 °C increase in the glass transition temperature of the daughter polymers. Subsequently, films were cast from solvents found suitable to forming self-assembled BCP thin films. The synthetic and processing approach allows for the formation of nanopatterned block copolymer films with controlled chemistries from a single source material. The BCPs were further characterized using water contact angle measurements and atomic force microscopy in liquid. Significantly decreased contact angles were caused by selective swelling of charged BCP domains. Protein (fibrinogen, albumin, cytochrome C, immunoglobulin G) adsorption experiments were conducted under static and dynamic conditions with a quartz crystal microbalance with dissipation. The results indicate that nanopatterned chemistry and experimental conditions strongly impact adsorption dynamics. Adsorption behavior was dependent both on protein structure and the characteristics of the surface. Depending on the structural stability

  18. Rheological and chemical evaluation on the ageing properties of SBS polymer modified bitumen: From the laboratory to the field

    NARCIS (Netherlands)

    Liu, G.; Nielsen, E.; Komacka, J.; Greet, L.; Ven, M.V.D.


    This study investigated the ageing properties of the styrene-butadiene- styrene polymer modified bitumen (SBS PMB) from the laboratory to the field. The virgin SBS PMB had been kept for 23 years and its field-aged binder was extracted from the reclaimed stone matrix asphalt (SMA) after the 22-year

  19. 75 FR 9438 - Americas Styrenics, LLC-Marietta Plant a Subsidiary of Americas Styrenics, LLLC Formerly Known as... (United States)


    ... Americas Styrenics LLC, including on- site leased workers from Pioneer Pipe Co., Marietta, Ohio. The notice... Employment and Training Administration Americas Styrenics, LLC-Marietta Plant a Subsidiary of Americas... Pioneer Pipe Co.: Marietta, OH; Amended Certification Regarding Eligibility To Apply for Worker Adjustment...

  20. Advanced analytical methods for the structure elucidation of polystyrene-b-poly(n-butyl acrylate) block copolymers prepared by reverse iodine transfer polymerisation

    Energy Technology Data Exchange (ETDEWEB)

    Wright, Trevor Gavin; Pfukwa, Helen; Pasch, Harald, E-mail:


    Reverse iodine transfer polymerisation (RITP) is a living radical polymerisation technique that has shown to be feasible in synthesising segmented styrene-acrylate copolymers. Polymers synthesised via RITP are typically only described regarding their bulk properties using nuclear magnetic resonance spectroscopy and size exclusion chromatography. To fully understand the complex composition of the polymerisation products and the RITP reaction mechanism, however, it is necessary to use a combination of advanced analytical methods. In the present RITP procedure, polystyrene was synthesised first and then used as a macroinitiator to synthesise polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers. For the first time, these PS-b-PBA block copolymers were analysed by a combination of SEC, in situ{sup 1}H NMR and HPLC. {sup 1}H NMR was used to determine the copolymer composition and the end group functionality of the samples, while SEC and HPLC were used to confirm the formation of block copolymers. Detailed information on the living character of the RITP process was obtained. - Highlights: • Comprehensive analysis of novel block copolymers. • Polymers were prepared for the first time by reverse iodine transfer polymerisation. • Combination of SEC, NMR, kinetic NMR, HPLC and comprehensive 2D-HPLC was used. • Detailed information about complex molecular composition and polymerisation kinetics was obtained.

  1. Grafting of styrene onto poly(vinylidene fluoride) films by gamma irradiation; Enxertia de estireno em filmes de poli(fluoreto de vinilideno) induzida por irradiacao gama

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, H.P.; Souza, C.P. de; Parra, D.F.; Lugao, A.B., E-mail: [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente


    Radiation induced grafting of styrene onto poly(vinylidene fluoride) (PVDF) was studied owing to the crescent interest in use of grafted films to produce membranes with ion exchange capability. A Cobalt-60 source was used, with doses of 5 and 10 kGy, at dose rate of 5 kGy.h{sup -1}, at room temperature, inert atmosphere and according to the simultaneous method. Solutions of styrene/toluene (1:1, v/v) and styrene/N,N-dimethylformamide (DMF) (1:1, v/v) were used. The films were characterized by FT-IR spectroscopy (Infrared Spectroscopy), Differential Scanning Calorimetry (DSC), Thermogravimetric Measurement (TG) and the degree of grafting (DOG) were calculated gravimetrically. Results shown that in studied conditions, DMF allow greatest DOG than toluene and that increasing the irradiation dose correspond an increase in DOG. Infrared and thermal analyses confirmed the presence in the grafted polymers. (author)

  2. Intrinsically Hierarchical Nanoporous Polymers via Polymerization-Induced Microphase Separation

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, Michael B.; Van Horn, J. David; Wu, Fei; Hillmyer, Marc A. (UMKC); (UMM)


    The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. Herein we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trapping of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.

  3. Kinetic Investigation of Styrene Free Radical Polymerization by Using Binary Mixtures of Monofunctional Initiators

    Directory of Open Access Journals (Sweden)

    Farshid Ziaee


    Full Text Available Polymerization of styrene in presence of two monofunctional initiators is studied kinetically in an ampoule scale. Polymerizations were ceased at different conversions for each ampoule while the temperature was increased almost linearly during the reaction. Three different initiator mixtures were used. The first mixtures were composed of benzoil peroxide (BPO and t-butyl perbenzoate (TBPB with various molar ratios and temperature programs. The second and third series were performed on mixtures of BPO and α,α'-azobisisobutyronitrile (AIBN and AIBN with TBPB, respectively. The experimental results for these series revealed thatincreasing the percentage of TBPB in the initiator mixtures at the same reaction temperature intervals enhanced polymerization rate and molecular weight of the resulting polymers. On the other hand the results from the second series indicated that reducing AIBN in the mixture would have reduction effect on the reaction temperatureintervals while both conversion and the polymer molecular weight are increased

  4. Thermo-Physical Properties of Kenaf-Filled Acrylonitrile Butadiene Styrene Composites

    Directory of Open Access Journals (Sweden)

    Nikmatin Siti


    Full Text Available Studies on advantageous of natural fillers incorporated into polymer composites on thermo-physical and mechanical properties are still intensively investigated. Several evidences suggest that the natural fillers with small contents combined with polymer increase their composite properties. We thus investigate thermo-physical properties of kenaf-filled acrylonitrile butadiene styrene (ABS composites. ABS with 5% kenaf microparticle size (ABS/K5, ABS with 5% kenaf short fiber (ABS/KSF5, and recycled ABS with 5% kenaf microparticle size (RABS/K5 were manufactured. Granular composites were manufactured by the twin screw extruder. Composite properties in terms of X-ray diffractions, surface morphologies, and thermal behaviors were investigated. The present work found that ABS/KSF5 has the highest degree of crystallinity compared to others. No significant difference was found in terms of thermal properties of the composites.

  5. Heterobimetallic coordination polymers based on the [Pt(SCN)4]2- and [Pt(SeCN)4]2- building blocks. (United States)

    Kobayashi, Masayuki; Savard, Didier; Geisheimer, Andrew R; Sakai, Ken; Leznoff, Daniel B


    New complexes and the first coordination polymers containing [Pt(SCN)4](2-) of the type [M(L)x][Pt(SCN)4] (where L = 2,2'-bipyridine (bipy), x = 2, M = Co(II), Ni(II), Cu(II); L = ethylenediamine (en), x = 2, M = Ni(II), Cu(II); L = N,N,N',N'-tetramethylethylenediamine (tmeda), x = 1, M = Cu(II); L = 2,2';6',2″-terpyridine (terpy), x = 1, M = Mn(II), Co(II); L = 1,10-phenanthroline (phen), x = 2, M = Pb(II)) were prepared by reacting the appropriate metal-ligand cations with K2[Pt(SCN)4] and structurally characterized. [M(bipy)2Pt(SCN)4]2·2MeOH (M = Co (1), Cu (4)) consist of supramolecular tetranuclear distorted squares containing two [M(bipy)2](2+) and two [Pt(SCN)4](2+) units. [Cu(bipy)2(NCS)]2[Pt(SCN)4] (6) is a double salt of the [Pt(SCN)4](2-) anion and two [Cu(bipy)(NCS)](+) cations. [Cu(en)2Pt(SCN)4] (7, 8) are 1-D coordination polymers that are coordinated in either cis or trans fashion at the [Pt(SCN)4](2-) unit, for 7 and 8, respectively. Complexes [Cu(en)2Pt(SeCN)4] (9) and [Ni(en)2Pt(SCN)4] (10) are similar to 8 and 7, respectively, but complex 9 (prepared using ((n)Bu4N)2[Pt(SeCN)4]) also presents intermolecular Se-Se interactions which resulted in an increased dimensionality. Compounds [M(terpy)Pt(SCN)4] (M = Mn (11), Co (13)) involve 2-D sheets of [M(terpy)](2+) and [Pt(SCN)4](2-) units, whereas [Mn(terpy)2][Pt(SCN)4] (12) is a double salt of one [Mn(terpy)2](2+) unit and one [Pt(SCN)4](2-). [Cu(tmeda)Pt(SCN)4] (14) contains a five-coordinate Cu(2+) metal center coordinated to one tmeda ligand and three different [Pt(SCN)4](2-) units, resulting in 2-D sheets. [Pb(phen)2Pt(SCN)4] (15) contains an 8-coordinate Pb(2+) metal center coordinated to two phen ligands and four [Pt(SCN)4](2-), generating a 3-D network in the solid state. Structural correlations were established between the ancillary ligand, the choice of metal, the structure of the [Pt(SCN)4](2-) building block, and the resulting dimensionality of the coordination polymers.

  6. Biocompatibility and characterization of polylactic acid/styrene-ethylene-butylene-styrene composites. (United States)

    Tsou, Chi-Hui; Kao, Bo-Jyue; Yang, Ming-Chien; Suen, Maw-Cherng; Lee, Yi-Hsuan; Chen, Jui-Chin; Yao, Wei-Hua; Lin, Shang-Ming; Tsou, Chih-Yuan; Huang, Shu-Hsien; De Guzman, Manuel; Hung, Wei-Song


    Polylactic acid (PLA)/styrene-ethylene-butylene-styrene (SEBS) composites were prepared by melt blending. Differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WXRD) were used to characterize PLA and PLA/SEBS composites in terms of their melting behavior and crystallization. Curves from thermal gravimetric analysis (TGA) illustrated that thermostability increased with SEBS content. Further morphological analysis of PLA/SEBS composites revealed that SEBS molecules were not miscible with PLA molecules in PLA/SEBS composites. The tensile testing for PLA and PLA/SEBS composites showed that the elongation at the break was enhanced, but tensile strength decreased with increasing SEBS content. L929 fibroblast cells were chosen to assess the cytocompatibility; the cell growth of PLA was found to decrease with increasing SEBS content. This study proposes possible reasons for these properties of PLA/SEBS composites.

  7. Neurobehavioral effects of acute styrene exposure in fiberglass boatbuilders

    Energy Technology Data Exchange (ETDEWEB)

    Letz, R.; Mahoney, F.C.; Hershman, D.L.; Woskie, S.; Smith, T.J. (Mount Sinai School of Medicine, New York, NY (USA))


    A field investigation of the effects of acute exposure to styrene among fiberglass boatbuilders was performed. Personal samples of styrene in breathing zone air and postshift urinary mandelic acid were collected for 105 workers exposed and not exposed to styrene in 6 fiberglass boatbuilding companies in New England. Three tests from the computerized Neurobehavioral Evaluation System (NES) were performed by the subjects in the morning before exposure to styrene, near midday, and at the end of the work day. Duration of exposure averaged 2.9 years (SD = 4.6), 8-hour TWA styrene exposure averaged 29.9 ppm (SD = 36.2), and urinary mandelic acid averaged 347 mg/g creatinine (SD = 465). Regression analyses indicated a statistically significant relationship between postshift performance on the Symbol-Digit test and both acute styrene exposure and mandelic acid. Other analyses comparing workers exposed to less than 50 ppm and greater than 50 ppm styrene also showed a significant effect on Symbol-Digit performance. All three NES tests showed test-retest correlation coefficients above .80, and ease of use for collection of neurobehavioral data under field conditions was demonstrated.

  8. Production and characterization of poly(styrene-co-methylmethacrylate);Producao e caracterizacao de poliestireno-co-metacrilato de metila

    Energy Technology Data Exchange (ETDEWEB)

    Augustinho, Tiago R.; Coan, Thais; Abarca, Silvia A.C.; Testoni, Alex A.S.; Baumgarten, Bruno P.; Machado, Ricardo A.F., E-mail: [Universidade Federal de Santa Catarina (UFSC), Florianopolis (Brazil). Dept. de Engenharia Quimica e Alimentos


    Polystyrene (PS) is a polymer used in diverse industrial segments. It is easy to process and has a low cost when compared to other materials. However, PS has low mechanical resistance, which limits its application in some areas. Thus, a methodology that is sufficiently used is the synthesis of a copolymer, formed of two or more monomers to get products that have characteristics that are not possible to obtain with only one monomer. In this work, the styrene and methyl methacrylate monomers had been carried through reactions of copolymerization by means of polymerization in suspension using (MMA) with styrene in a bigger percentage. MMA was selected for being a monomer that results in a polymeric configuration more resistant than the PS. The copolymerization was proven to occur by infra-red spectroscopy (IR) and Nuclear Magnetic Resonance (NMR). Different analyses were performed using different initiators, weight molar and conversion studies. (author)

  9. Copper mediated controlled radical copolymerization of styrene and2-ethylhexyl acrylate and determination of their reactivity ratios.

    Directory of Open Access Journals (Sweden)

    Bishnu Prasad Koiry


    Full Text Available Copolymerization is an important synthetic tool to prepare polymers with desirable combination of properties which are difficult to achieve from the different homopolymers concerned. This investigation reports the copolymerization of 2-ethylhexyl acrylate (EHA and styrene using copper bromide (CuBr as catalyst in combination with N,N,N’,N,N- pentamethyldiethylenetriamine (PMDETA as ligand and 1-phenylethyl bromide (PEBr as initiator. Linear kinetic plot and linear increase in molecular weights versus conversion indicate that copolymerization reactions were controlled. The copolymer composition was calculated using 1H NMR studies. The reactivity ratio of styrene and EHA (r1 and r2 were determined using the Finemann-Ross (FR, inverted Finemann-Ross (FR and Kelen-Tudos (KT methods. Thermal properties of the copolymers were also studied by using TGA and DSC analysis.

  10. A Facile Approach Toward Scalable Fabrication of Reversible Shape-Memory Polymers with Bonded Elastomer Microphases as Internal Stress Provider. (United States)

    Fan, Long Fei; Rong, Min Zhi; Zhang, Ming Qiu; Chen, Xu Dong


    The present communication reports a novel strategy to fabricate reversible shape-memory polymer that operates without the aid of external force on the basis of a two-phase structure design. The proof-of-concept material, crosslinked styrene-butadiene-styrene block copolymer (SBS, dispersed phase)/polycaprolactone-based polyurethane (PU, continuous phase) blend, possesses a closely connected microphase separation structure. That is, SBS phases are chemically bonded to crosslinked PU by means of a single crosslinking agent and two-step crosslinking process for increasing integrity of the system. Miscibility between components in the blend is no longer critical by taking advantage of the reactive blending technique. It is found that a suitable programming leads to compressed SBS, which serves as internal expansion stress provider as a result. The desired two-way shape-memory effect is realized by the joint action of the temperature-induced reversible opposite directional deformabilities of the crystalline phase of PU and compressed SBS, accompanying melting and orientated recrystallization of the former. Owing to the broadness of material selection and manufacturing convenience, the proposed approach opens an avenue toward mass production and application of the smart polymer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Evolution of entanglements during the response to a uniaxial deformation of lamellar triblock copolymers and polymer glasses. (United States)

    Léonforte, F


    Using coarse-grained molecular-dynamics simulations, a generic styrene-block-butadiene-block-styrene triblock copolymer under lamellar conformation is used in order to investigate the mutual entanglement evolution when a structure of alternating glassy (S)/rubbery (B) layers is submitted to an imposed deformation. By varying the amount of loop chains between each phase, i.e., noncrossing chains, it is possible to generate different types of S/B interface definitions. A specific boundary driven tensile strain protocol has been developed in order to mimic "real" experiments and measure the stress-strain curve. The same protocol is also applied to a reference state consisting in a directed glassy homopolymers, as well as to an isotropic glassy polymer. The evolution of initial mutual entanglements from the undeformed samples during the whole deformation process is monitored. It is shown for all considered systems that initial entanglements mostly participate to the preyield regime of the stress-strain curve and that this network is debonded during the strain-hardening regime. For triblocks with a non-null amount of crossing chains, the lower the amount is, the longer the memory effect of the initial entanglement network in the postyield regime is. On the fly distributions of entanglements, which depart from the postyield regime, depict memory effects and long-time correlations during the strain-hardening regime. For triblocks, loop chains reinforce these effects.

  12. Proton conducting sulphonated fluorinated poly(styrene) crosslinked electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Soules, A.; Ameduri, B.; Boutevin, B.; David, G. [Institut Charles Gerhardt UMR CNRS 5253 Equipe, Ingenierie et Architectures Macromoleculaires,' ' Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de l' Ecole Normale, 34296 Montpellier, Cedex 05 (France); Perrin, R. [CEA Le Ripault Departement des Materiaux, DMAT/SCMF/LSTP, BP16 - 37260 Monts (France); Gebel, G. [Structure et Proprietes des Architectures Moleculaires UMR 5819 (CEA-CNRS-UJF), INAC, SPrAM, CEA Grenoble, 17 Rue des Martyrs, 38054 Grenoble, Cedex 9 (France)


    Potential membranes for polymer electrolyte membrane fuel cell based on crosslinked sulphonated fluorinated polystyrenes (PS) were synthesised in two steps. First, azide-telechelic polystyrene was obtained by iodine transfer polymerisation of styrene in the presence of 1,6-diiodoperfluorohexane followed by azido chain-end functionalisation. Then azide-telechelic polystyrene was efficiently crosslinked with 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane under UV irradiation. After 45 min only, almost completion of azide crosslinking could be achieved, resulting in crosslinked membranes with insoluble fractions higher than 95%. The sulphonation of the crosslinked membranes afforded ionic exchange capacities (IECs) ranging from 2.2 to 3.2 meq g{sup -1}. The hydration number was shown to be very high (from 30 to 75), depending on both the content of perfluorodecane and of sulphonic acid groups. The morphology of the membranes, assessed by small-angle X-ray scattering, was found to be a lamellar-type structure with two types of ionic domains. For the membrane that exhibited an IEC value of 2.2 meq.g{sup -1}, proton conductivity was in the same range as that of Nafion {sup registered} (120-135{sup -1}), whereas the membrane IEC value of 3.2 meq.g{sup -1} showed a proton conductivity higher than that of Nafion {sup registered} in liquid water from 25 to 80 C, though a high water uptake. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films (United States)

    Zorn, Gilad; Migonney, Véronique; Castner, David G.


    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

  14. Preliminary study of styrene grafting on polyethylene films

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Gilberto de O.; Geraldes, Adriana N.; Zen, Heloisa A.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], E-mail:


    Grafting of styrene on polyethylene was carried out as a preliminary study. The experiments covered a range from 5 to 20 kGy and intended to evaluate the absorbed dose that led to the best degree of grafting (DOG) under industrial dose rate. PE films 0,065 mm thick were exposed several times to radiation at room temperature and nitrogen atmosphere. The films were immersed in the solution content styrene/solvent then irradiated (5 to 20 kGy) dose. As an exploratory experiment, styrene grafting was gravimetrically evaluated and characterized by infrared spectroscopy (FTIR).The degree of grafting (DOG) was calculated. Concentrations of methanol/ Styrene at the rate of 80:20 were favorable at low dose of 10 kGy. In presence of acid, best result was achieved at 15 kGy in the range of 5 to 20 kGy. (author)

  15. Relation between colour vision loss and occupational styrene exposure level


    Gong, Y; Kishi, R.; Katakura, Y; Tsukishima, E; Fujiwara, K.; Kasai, S; Satoh, T.; Sata, F; Kawai, T.


    Aims: To investigate the relation between colour vision loss and the exposure level of styrene. Exposure level included the current exposure concentration, past cumulative exposure, and the maximum exposure level in the past.

  16. Dynamic response of acrylonitrile butadiene styrene under impact loading

    National Research Council Canada - National Science Library

    Owolabi, Gbadebo; Peterson, Alex; Habtour, Ed; Riddick, Jaret; Coatney, Michael; Olasumboye, Adewale; Bolling, Denzell


    ... rateloading.Tensile tests were conducted on 3-D printed acrylonitrile butadiene styrene (ABS) at differentstrain rates, according to the ASTM D638 standard, to assess its strain rate sensitivity under quasi-staticloads...

  17. End-Functionalized Polymers and Junction-Functionalized Diblock Copolymers Via RAFT Chain Extension with Maleimido Monomers (United States)

    Henry, Scott M.; Convertine, Anthony J.; Benoit, Danielle S. W.; Hoffman, Allan S.; Stayton, Patrick S.


    A new strategy is described for functionalizing the ω-terminal end of polymers synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization that provides spatially controlled bioconjugation sites. Traditional methods for preparing ω-functional polymers require the reduction of the RAFT chain-transfer agent to yield secondary or tertiary thiols of low reactivity or the synthesis of novel chain-transfer agents that contain reactive groups. As an additional strategy, N-substituted maleimido monomers have been used in a modified block polymerization to add a single maleimido unit onto the RAFT polymer with nearly quantitative efficiency. Unique reactive groups contained in the N-substituent are thereby added to the ω-terminal end of the polymer and are subsequently available for conjugation reactions. This technique has been demonstrated using N-(2-aminoethyl)maleimide trifluoroacetate to introduce a single primary amine to the ω-terminus of poly(dimethy-laminoethyl methacrylate) and poly(N-isopropyl acrylamide) and to a specialized block copolymer for siRNA delivery. Evidence for retention of functional RAFT endgroups is provided by synthesis results where chain-extended polyDMAEMA (Mn = 10 600 g/mol, Mw/Mn = 1.14) was used as a macro chain transfer agent for the polymerization of styrene, yielding a diblock polymer of low polydispersity (Mn = 20 300 g/mol, Mw/Mn = 1.11). It is thus also possible to construct diblock copolymers with a bioconjugation site precisely located at the junction between the two blocks. The chain-extended polymers are functionalized with an amine-reactive fluorescent dye or folic acid at conjugation efficiencies of 86 and 94%, respectively. The versatile chain-extension technique described here offers unique opportunities for the synthesis of well-defined polymeric conjugates to molecules of biological and targeting interest. PMID:19480416

  18. Styrene-Associated Health Outcomes at a Windblade Manufacturing Plant (United States)

    McCague, Anna-Binney; Cox-Ganser, Jean M.; Harney, Joshua M.; Alwis, K. Udeni; Blount, Benjamin C.; Cummings, Kristin J.; Edwards, Nicole; Kreiss, Kathleen


    Background Health risks of using styrene to manufacture windblades for the green energy sector are unknown. Methods Using data collected from 355 (73%) current windblade workers and regression analysis, we investigated associations between health outcomes and styrene exposure estimates derived from urinary styrene metabolites. Results The median current styrene exposure was 53.6 mg/g creatinine (interquartile range: 19.5–94.4). Color blindness in men and women (standardized morbidity ratios 2.3 and 16.6, respectively) was not associated with exposure estimates, but was the type previously reported with styrene. Visual contrast sensitivity decreased and chest tightness increased (odds ratio 2.9) with increasing current exposure. Decreases in spirometric parameters and FeNO, and increases in the odds of wheeze and asthma-like symptoms (odds ratios 1.3 and 1.2, respectively) occurred with increasing cumulative exposure. Conclusions Despite styrene exposures below the recommended 400 mg/g creatinine, visual and respiratory effects indicate the need for additional preventative measures in this industry. PMID:26305283

  19. Proton conductive membranes based on poly (styrene-co-allyl alcohol semi-IPN

    Directory of Open Access Journals (Sweden)

    Felipe Augusto Moro Loureiro


    Full Text Available The optimization of fuel cell materials, particularly polymer membranes, for PEMFC has driven the development of methods and alternatives to achieve systems with more adequate properties to this application. The sulfonation of poly (styrene-co-allyl alcohol (PSAA, using sulfonating agent:styrene ratios of 2:1, 1:1, 1:2, 1:4, 1:6, 1:8 and 1:10, was previously performed to obtain proton conductive polymer membranes. Most of those membranes exhibited solubility in water with increasing temperature and showed conductivity of approximately 10-5 S cm-1. In order to optimize the PSAA properties, especially decreasing its solubility, semi-IPN (SIPN membranes are proposed in the present study. These membranes were obtained from the diglycidyl ether of bisphenol A (DGEBA, curing reactions in presence of DDS (4,4-diaminodiphenyl sulfone and PSAA. Different DGEBA/PSAA weight ratios were employed, varying the PSAA concentration between 9 and 50% and keeping the mass ratio of DGEBA:DDS as 1:1. The samples were characterized by FTIR and by electrochemical impedance spectroscopy. Unperturbed bands of PSAA were observed in the FTIR spectra of membranes, suggesting that chemical integrity of the polymer is maintained during the synthesis. In particular, bands involving C-C stretching (1450 cm-1, C=C (aromatic, ~ 3030 cm-1 and C-H (2818 and 2928 cm-1 were observed, unchanged after the synthesis. The disappearance or reduction of the intensity of the band at 916 cm-1, attributed to the DGEBA epoxy ring, is evidenced for all samples, indicating the epoxy ring opening and the DGEBA crosslinking. Conductivity of H3PO4 doped membranes increases with temperature, reaching 10-4 S cm-1.

  20. Experimental Investigations on Tribological Behaviour of Alumina Added Acrylonitrile Butadiene Styrene (ABS Composites

    Directory of Open Access Journals (Sweden)

    T. Panneerselvam


    Full Text Available Composite materials are multifunctional in nature, which can be custom-made based on the nature of the applications. The challenge of composite materials lie on complementing the properties of one another i.e. materials which go in the making of composites strengthen each other by inhibiting their weaknesses. Polymers are one of the widely used materials which serve a wide spectrum of engineering needs. In the present work, the tribological behaviour of a composite containing Acrylonitrile Butadiene Styrene (ABS and traces of Alumina is experimentally investigated. Alumina is added to ABS in various percentages such as 1%, and 3% by weight in order to improve the wear resistance of the polymer. Central Composite Design was used to design the experiments and a standard Pin-On-Disk apparatus was used to conduct the experiments. It is observed from the test results that the addition of alumina significantly enhances the wear behavior of the polymer. However, adding more percentage of alumina has led to adverse effect on wear resistance of polymer materials. Abrasive wear mechanism is found to be predominant in the case of alumina added composite materials. It is also found that 1% alumina added composite exhibits excellent wear properties compared to other materials.

  1. Superhydrophilic poly (styrene co acrylonitrile)-ZnO nanocomposite surfaces for UV shielding and self-cleaning applications (United States)

    Singh, Rajender; Sharma, Ramesh; Barman, P. B.; Sharma, Dheeraj


    UV shielding based super hydrophilic material is developed in the present formulation by in situ emulsion polymerization of poly (styrene-acrylonitrile) with ZnO nanoparticles. The ESI-MS technique confirms the structure of polymer nanocomposite by their mass fragments. The XRD study confirms the presence of ZnO phase in polymer matrix. PSAN/ZnO nanocomposite leads to give effective UV shielding (upto 375 nm) and visible luminescence with ZnO content in polymer matrix. The FESEM and TEM studies confirm the symmetrical, controlled growth of PNs. The incorporation of ZnO nanofillers into PSAN matrix lead to restructuring the PNs surfaces into superhydrophilic surfaces in water contact angle (WCA) from 70° to 10°. We believe our synthesized PSAN/ZnO nanocomposite could be potential as UV shielding, luminescent and super hydrophilic nature based materials in related commercial applications.

  2. Indolo-naphthyridine-6,13-dione Thiophene Building Block for Conjugated Polymer Electronics: Molecular Origin of Ultrahigh n-Type Mobility

    KAUST Repository

    Fallon, Kealan J.


    Herein, we present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm V s. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. OPV device efficiencies up to 4.1% and charge photogeneration up to 1000 nm are demonstrated, highlighting the potential of this novel chromophore class in high-performance organic electronics.


    Directory of Open Access Journals (Sweden)

    G. T. Justino

    Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

  4. Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature. (United States)

    Hansch, Markus; Hämisch, Benjamin; Schweins, Ralf; Prévost, Sylvain; Huber, Klaus


    The dilute solution behavior of sodium poly(styrene sulfonate) is studied in the presence of trivalent Al3+ and bivalent Ba2+ cations at various levels of excess NaCl. The study evaluates the phase behavior and the morphology of the polyelectrolyte chains with increasing extent of decoration with the Al3+ and Ba2+ cations and analyses the effect of temperature on these decorated chains. The phase behavior is presented in the form of the cation concentration versus the respective poly(styrene sulfonate) concentration, recorded at the onset of precipitation. Whereas poly(styrene sulfonate) with Al3+ exhibits a linear phase boundary, denoted as the "threshold line," which increases with increasing poly(styrene sulfonate) concentration, Ba2+ cations show a threshold line which is independent of the poly(styrene sulfonate) concentration. An additional re-entrant phase, at considerably higher cation content than those of the threshold lines, is observed with Al3+ cations but not with Ba2+ cations. The threshold line and the re-entrant phase boundary form parts of the liquid-liquid phase boundary observed at the limit of low polymer concentration. The dimensions of the polyelectrolyte chains shrink considerably while approaching the respective threshold lines on increase of the Al3+ and Ba2+ cation content. However, subtle differences occur between the morphological transformation induced by Al3+ and Ba2+. Most strikingly, coils decorated with Al3+ respond very differently to temperature variations than coils decorated with Ba2+ do. As the temperature increases, the poly(styrene sulfonate) chains decrease their size in the presence of Al3+ cations but increase in size in the presence of Ba2+ cations.

  5. [Styrene migration into wine contained in polyester resin tanks]. (United States)

    Giffone, M; Brun, S


    The use of polyester resins in wine tanks manufacture or coating has widely spread during the past five years; this type of material has been and is still the source of organoleptic damage due to non polymerized sytrene migration into urine. Sytrene is a solvant often used in resin polymerization: it act as a reticulation agent of insaturated linear polyester. Polymerization at room temperature is allowed gy additives but has to be completed in warm air or in steam. An excess of styrene is often used for a polymerisation as complete as possible and remains on a free form. Then it migrates from the tank walls into the wine. For a better understanding of the styrene migration mechanism studies were performed on two levels: from small containers (4 l) kept in the laboratory and from tanks (30 hl) set up in an I.N.R.A. wine estate in all conditions usually realized in practice. Influence of time, temperature and alcohol content were studied. Styrene migration was interpreted as a diffusion phenomenom and styrene diffusion coefficients were calculated for several temperatures. Knowledge of these coefficients and of styrene content of the tank walls allow the prediction of a tank behaviour in time. Other substances that styrene were detected in wine and in tank walls, they are impurities either from resins like ethylbenzene, or from the catalyst like mesityl oxide. The lattest has never been mentioned in the litterature. From the results obtained it is possible to give some advices to manufacturers and users of polyester resin tanks, about the quality of raw materials, resins and additives along with the conditions carried and for their use and about the control of monomer styrene content in the walls of just manufactured tank.

  6. Fabrication of Acrylonitrile-Butadiene-Styrene Nanostructures with Anodic Alumina Oxide Templates, Characterization and Biofilm Development Test for Staphylococcus epidermidis.

    Directory of Open Access Journals (Sweden)

    Camille Desrousseaux

    Full Text Available Medical devices can be contaminated by microbial biofilm which causes nosocomial infections. One of the strategies for the prevention of such microbial adhesion is to modify the biomaterials by creating micro or nanofeatures on their surface. This study aimed (1 to nanostructure acrylonitrile-butadiene-styrene (ABS, a polymer composing connectors in perfusion devices, using Anodic Alumina Oxide templates, and to control the reproducibility of this process; (2 to characterize the physico-chemical properties of the nanostructured surfaces such as wettability using captive-bubble contact angle measurement technique; (3 to test the impact of nanostructures on Staphylococcus epidermidis biofilm development. Fabrication of Anodic Alumina Oxide molds was realized by double anodization in oxalic acid. This process was reproducible. The obtained molds present hexagonally arranged 50 nm diameter pores, with a 100 nm interpore distance and a length of 100 nm. Acrylonitrile-butadiene-styrene nanostructures were successfully prepared using a polymer solution and two melt wetting methods. For all methods, the nanopicots were obtained but inside each sample their length was different. One method was selected essentially for industrial purposes and for better reproducibility results. The flat ABS surface presents a slightly hydrophilic character, which remains roughly unchanged after nanostructuration, the increasing apparent wettability observed in that case being explained by roughness effects. Also, the nanostructuration of the polymer surface does not induce any significant effect on Staphylococcus epidermidis adhesion.

  7. Fabrication of Acrylonitrile-Butadiene-Styrene Nanostructures with Anodic Alumina Oxide Templates, Characterization and Biofilm Development Test for Staphylococcus epidermidis. (United States)

    Desrousseaux, Camille; Cueff, Régis; Aumeran, Claire; Garrait, Ghislain; Mailhot-Jensen, Bénédicte; Traoré, Ousmane; Sautou, Valérie


    Medical devices can be contaminated by microbial biofilm which causes nosocomial infections. One of the strategies for the prevention of such microbial adhesion is to modify the biomaterials by creating micro or nanofeatures on their surface. This study aimed (1) to nanostructure acrylonitrile-butadiene-styrene (ABS), a polymer composing connectors in perfusion devices, using Anodic Alumina Oxide templates, and to control the reproducibility of this process; (2) to characterize the physico-chemical properties of the nanostructured surfaces such as wettability using captive-bubble contact angle measurement technique; (3) to test the impact of nanostructures on Staphylococcus epidermidis biofilm development. Fabrication of Anodic Alumina Oxide molds was realized by double anodization in oxalic acid. This process was reproducible. The obtained molds present hexagonally arranged 50 nm diameter pores, with a 100 nm interpore distance and a length of 100 nm. Acrylonitrile-butadiene-styrene nanostructures were successfully prepared using a polymer solution and two melt wetting methods. For all methods, the nanopicots were obtained but inside each sample their length was different. One method was selected essentially for industrial purposes and for better reproducibility results. The flat ABS surface presents a slightly hydrophilic character, which remains roughly unchanged after nanostructuration, the increasing apparent wettability observed in that case being explained by roughness effects. Also, the nanostructuration of the polymer surface does not induce any significant effect on Staphylococcus epidermidis adhesion.

  8. Spectrophotometric study of the interaction of methylene blue with poly(styrene-co-sodium styrene sulfonate

    Directory of Open Access Journals (Sweden)

    Souha Ben Mahmoud


    Full Text Available The interaction of the cationic phenothiazine dye, the Methylene Blue (MB with poly-(sodium styrene sulfonatef–co-(styrene1-f, (PSSNa f, has been investigated by spectrophotometric method. The polyelectrolyte induced metachromasy resulting in a blue shift of the absorption maxima of the dye, in agreement with the formation of dye H-aggregates. The stability of the PSSNa-MB complexes was studied as a function of polyelectrolyte chain length, polyelectrolyte electrostatic charge density f, polyelectrolyte concentration, NaCl salt addition, tetrahydrofurane (THF addition and THF treatment. The stoichiometry of PSSNa-MB complex evaluated by the molar ratio method was found 4:1 for the fully charged PSSNa f = 1. Reversal of metachromasy was observed upon salt and THF addition, while THF treatment does not affect the complex and allows recovering the initial complex. Finally, thermodynamic parameters of the interaction between the polyelectrolyte and the dye at different temperatures, namely free energy DG, the enthalpy DH and the entropy DS have been evaluated to determine the binding constant and as a consequence the stability of the complex. The metachromasy effect was found to be more high as the chemical charge f increases and reaches its maximum value f = 1, when operating at optimal conditions. So, the PSSNa f = 1-MB complex is the most stable in comparison to the others based on lower charge density PSSNa f.

  9. Preparation, characterization and conductivity study of nitro-mercurated styrene butadiene rubber/silver doped zinc oxide nanocomposites (United States)

    Anilkumar, T.; Naik, Adarsh Ajith; Ramesan, M. T.


    Here we report the preparation of nitromercurated styrene butadiene rubber (NMSBR)/silver doped zinc oxide nanocomposite by inexpensive and ecofriendly two roll mill mixing. The composites were characterized by UV, FTIR, XRD, SEM, TGA and conductivity measurements. UV and FTIR spectrum indicated the interfacial interaction between the polymer and nanoparticles.XRD and SEM images showed the uniform arrangement of nanoparticles within the macromolecular chain. TGA study indicated the better thermal resistance of the composite. The dielectric properties and AC conductivity ofnanocomposites were much greater than nitromercurated SBR and they may be used as multifunctional materials for nanoelectronic devices.

  10. Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno The use of nickel-based catalysts for homo-and copolymerization of styrene

    Directory of Open Access Journals (Sweden)

    Luis Carlos Ferreira Jr.


    Full Text Available This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO, have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

  11. Designing N-halamine based antibacterial surface on polymers: Fabrication, characterization, and biocidal functions (United States)

    Chen, Yong; Han, Qiuxia


    We demonstrate a valuable method to generate reactive groups on inert polymer surfaces and bond antibacterial agents for biocidal ability. Polystyrene (PS) surfaces were functionalized by spin coating of sub-monolayer and monolayer films of poly(styrene- b- tert-butyl acrylate) (PS-P tBA) block copolymer from solutions in toluene. PS-P tBA self-assembled to a bilayer structure on PS that contains a surface layer of the P tBA blocks ordering at the air-polymer interface and a bottom layer of the PS blocks entangling with the PS substrate. The thickness of P tBA layer could be linearly controlled by the concentration of the spin coating solution and a 2.5 nm saturated monolayer coverage of P tBA was achieved at 0.35% (w/w). Carboxyl groups were generated by exposing the tert-butyl ester groups of P tBA on saturated surface to trifluoroacetic acid (TFA) to bond tert-butylamine via amide bonds that were further chlorinated to N-halamine with NaOCl solution. The density of N-halamine on the chlorinated surface was calculated to be 1.05 × 10 -5 mol/m 2 by iodimetric/thiosulfate titration. Presented data showed the N-halamine surface provided powerful antibacterial activities against Staphylococcus aureus and Escherichia coli. Over 50% of the chlorine lost after UVA irradiation could be regained upon rechlorination. This design concept can be virtually applied to any inert polymer by choosing appropriate block copolymers and antibacterial agents to attain desirable biocidal activity.

  12. Designing N-halamine based antibacterial surface on polymers: Fabrication, characterization, and biocidal functions

    Energy Technology Data Exchange (ETDEWEB)

    Chen Yong, E-mail: [Department of Applied Chemistry, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, 579 Qianwangang Rd., Huangdao Zone, Qingdao 266510 (China); Han Qiuxia [Department of Biological Engineering, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266510 (China)


    We demonstrate a valuable method to generate reactive groups on inert polymer surfaces and bond antibacterial agents for biocidal ability. Polystyrene (PS) surfaces were functionalized by spin coating of sub-monolayer and monolayer films of poly(styrene-b-tert-butyl acrylate) (PS-PtBA) block copolymer from solutions in toluene. PS-PtBA self-assembled to a bilayer structure on PS that contains a surface layer of the PtBA blocks ordering at the air-polymer interface and a bottom layer of the PS blocks entangling with the PS substrate. The thickness of PtBA layer could be linearly controlled by the concentration of the spin coating solution and a 2.5 nm saturated monolayer coverage of PtBA was achieved at 0.35% (w/w). Carboxyl groups were generated by exposing the tert-butyl ester groups of PtBA on saturated surface to trifluoroacetic acid (TFA) to bond tert-butylamine via amide bonds that were further chlorinated to N-halamine with NaOCl solution. The density of N-halamine on the chlorinated surface was calculated to be 1.05 x 10{sup -5} mol/m{sup 2} by iodimetric/thiosulfate titration. Presented data showed the N-halamine surface provided powerful antibacterial activities against Staphylococcus aureus and Escherichia coli. Over 50% of the chlorine lost after UVA irradiation could be regained upon rechlorination. This design concept can be virtually applied to any inert polymer by choosing appropriate block copolymers and antibacterial agents to attain desirable biocidal activity.

  13. Preparing cellulose nanocrystal/acrylonitrile-butadiene-styrene nanocomposites using the master-batch method. (United States)

    Ma, Libo; Zhang, Yang; Meng, Yujie; Anusonti-Inthra, Phuriwat; Wang, Siqun


    The master-batch method provides a simple way to apply cellulose nanocrystal (CNC) as reinforcement in a hydrophobic matrix. The two-stage process includes making high-CNC content (70 wt%) master batch pellets, then mixing acrylonitrile-butadiene-styrene (ABS) and maleic anhydride grafted polyethylene with the master batch pellets to prepare the ABS/CNC nanocomposite in extruder. SEM image indicates that self-assembled CNC nanosheets disperse evenly throughout the polymer matrix. The improved mechanical properties shown in tensile and DMA tests reveal that the CNC combines well with the ABS. TGA results show that the thermal degradation temperature of CNC in the master batch increases because of the protection of the ABS coating. This approach not only improves the dispersion ability and the thermal stability of CNC, but it is also applicable to use with other hydrophobic thermoplastics in industrial scale production. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Performance of asphaltic concrete incorporating styrene butadiene rubber subjected to varying aging condition (United States)

    Salah, Faisal Mohammed; Jaya, Ramadhansyah Putra; Mohamed, Azman; Hassan, Norhidayah Abdul; Rosni, Nurul Najihah Mad; Mohamed, Abdullahi Ali; Agussabti


    The influence of styrene butadiene rubber (SBR) on asphaltic concrete properties at different aging conditions was presented in this study. These aging conditions were named as un-aged, short-term, and long-term aging. The conventional asphalt binder of penetration grade 60/70 was used in this work. Four different levels of SBR addition were employed (i.e., 0 %, 1 %, 3 %, and 5 % by binder weight). Asphalt concrete mixes were prepared at selected optimum asphalt content (5 %). The performance was evaluated based on Marshall Stability, resilient modulus, and dynamic creep tests. Results indicated the improving stability and permanent deformation characteristics that the mixes modified with SBR polymer have under aging conditions. The result also showed that the stability, resilient modulus, and dynamic creep tests have the highest rates compared to the short-term aging and un-aged samples. Thus, the use of 5 % SBR can produce more durable asphalt concrete mixtures with better serviceability.

  15. Regenerated thermosetting styrene-co-acrylonitrile sandwich ...

    Indian Academy of Sciences (India)

    ... 2 Qin Peng1 2 Anrong Zeng1 2 Junlin Li1 2 Xiaole Wu1 2 Xiaofei Liu1 2. Department of Polymer Materials Science and Engineering, College of Materials Science and Engineering, Tianjin University, Weijin Road 92, Nankai District, Tianjin 300072, PR China; Tianjin Key Laboratory of Composite and Functional Materials, ...

  16. The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers (United States)

    Moussa, Mehdi Elsayed; Attenberger, Bianca; Fleischmann, Martin; Schreiner, Andrea


    The three‐component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with Ag[BF4] (2) in the presence of 2,2′‐bipyrimidine (3) leads to the formation of the two novel two‐dimensional networks 4 and 5. Compound 4 is a new two‐dimensional organometallic‐organic hybrid polymer, while derivative 5 represents a unique two‐dimensional organometallic‐inorganic‐organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two‐component reactions with organic molecules in addition of metal ions. PMID:27867315

  17. Environmental stress cracking of polymers (United States)

    Mahan, K. I.


    A two point bending method for use in studying the environmental stress cracking and crazing phenomena is described and demonstrated for a variety of polymer/solvent systems. Critical strain values obtained from these curves are reported for various polymer/solvent systems including a considerable number of systems for which critical strain values have not been previously reported. Polymers studied using this technique include polycarbonate (PC), ABS, high impact styrene (HIS), polyphenylene oxide (PPO), and polymethyl methacrylate (PMMA). Critical strain values obtained using this method compared favorably with available existing data. The major advantage of the technique is the ability to obtain time vs. strain curves over a short period of time. The data obtained suggests that over a short period of time the transition in most of the polymer solvent systems is more gradual than previously believed.

  18. Analysis of Mechanical and Thermogravimetric Properties of Composite Materials Based on PVA/MWCNT and Styrene-Acrylic Copolymer/MWCNT (United States)

    Volynets, N. I.; Poddubskaya, O. G.; Demidenko, M. I.; Lyubimov, A. G.; Kuzhir, P. P.; Suslyaev, V. I.; Pletnev, M. A.; Zicans, Janis


    Mechanical and thermogravimetric properties of polymer composite materials with various concentrations of multiwalled carbon nanotubes effectively shielding radiation in the radio frequency (20 Hz - 1 MHz) and microwave (26-36 GHz) frequency ranges are studied. As a matrix, widely available polymeric materials, such as polyvinyl acetate and styrene-acrylate, were used in the form of dispersions. From the analysis of the obtained experimental data, it was shown that the introduction of carbon nanotubes into the polymer matrix makes it possible to increase mechanical properties and thermal stability of composite materials.

  19. Conceptual process design of extractive distillation processes for ethylbenzene/styrene separation

    NARCIS (Netherlands)

    Jongmans, Mark; Hermens, E.; Raijmakers, M.; Maassen, J.I.W.; Schuur, Boelo; de Haan, A.B.


    In the current styrene production process the distillation of the close-boiling ethylbenzene/styrene mixture to obtain an ethylbenzene impurity level of 100 ppm in styrene accounts for 75–80% of the energy requirements. The future target is to reach a level of 1–10 ppm, which will increase the

  20. Controlled Functionalization of Olefin/styrene Copolymers through Free Radical Processes

    NARCIS (Netherlands)

    Passaglia, Elisa; Aglietto, Mauro; Ciardelli, Francesco; Picchioni, Francesco


    The functionalization of styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) and styrene-co-butadiene (SBR) random copolymer by free radical processes is presented. SEBS was functionalized in the melt with diethyl maleate (DEM) and dicumyl peroxide (DCP) as initiator. The

  1. 21 CFR 177.1040 - Acrylonitrile/styrene copoly-mer. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/styrene copoly-mer. 177.1040 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1040 Acrylonitrile/styrene copoly-mer. Acrylonitrile/styrene copolymers identified in this section may be safely used as a component...

  2. In vitro evolution of styrene monooxygenase from Pseudomonas putida CA-3 for improved epoxide synthesis

    NARCIS (Netherlands)

    Gursky, Lucas J.; Nikodinovic-Runic, Jasmina; Feenstra, K Anton; O'Connor, Kevin E.


    The styAB genes from Pseudomonas putida CA-3, which encode styrene monooxygenase, were subjected to three rounds of in vitro evolution using error-prone polymerase chain reaction with a view to improving the rate of styrene oxide and indene oxide formation. Improvements in styrene monooxygenase

  3. RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

    Directory of Open Access Journals (Sweden)

    Lin Wu


    Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

  4. Artificially Engineered Protein Polymers. (United States)

    Yang, Yun Jung; Holmberg, Angela L; Olsen, Bradley D


    Modern polymer science increasingly requires precise control over macromolecular structure and properties for engineering advanced materials and biomedical systems. The application of biological processes to design and synthesize artificial protein polymers offers a means for furthering macromolecular tunability, enabling polymers with dispersities of ∼1.0 and monomer-level sequence control. Taking inspiration from materials evolved in nature, scientists have created modular building blocks with simplified monomer sequences that replicate the function of natural systems. The corresponding protein engineering toolbox has enabled the systematic development of complex functional polymeric materials across areas as diverse as adhesives, responsive polymers, and medical materials. This review discusses the natural proteins that have inspired the development of key building blocks for protein polymer engineering and the function of these elements in material design. The prospects and progress for scalable commercialization of protein polymers are reviewed, discussing both technology needs and opportunities.

  5. Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics

    KAUST Repository

    Zhang, Zhen


    Aggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom transfer radical copolymerization (ATRP) of a double styrene-functionalized tetraphenylethene (TPE-2St) used as a cross-linker with linear arm precursors possessing terminal ATRP initiating moieties. Polyethylene macroinitiator (PE–Br) was prepared via the polyhomologation of dimethylsulfoxonium methylide with triethylborane followed by oxidation/hydrolysis and esterification of the produced PE–OH with 2-bromoisobutyryl bromide; polyethylene-block-poly(ε-caprolactone) diblock macroinitiator was derived by combining polyhomologation with ring-opening polymerization (ROP). All synthesized star polymers showed AIE-behavior either in solution or in bulk. At high concentration in good solvents (e.g., THF, or toluene) they exhibited low photoluminescence (PL) intensity due to the inner filter effect. In sharp contrast to the small molecule TPE-2St, the star polymers were highly emissive in dilute THF solutions. This can be attributed to the cross-linked structure of poly(TPE-2St) core which restricts the intramolecular rotation and thus induces emission. In addition, the PL intensity of PE star polymers in THF(solvent)/n-hexane(nonsolvent) mixtures, due to their nearly spherical shape, increased when the temperature decreased from 55 to 5 °C with a linear response in the range 40–5 °C.

  6. Reclamation of post-consumer plastics for development of polycarbonate and acrylonitrile butadiene styrene based nanocomposites with nanoclay (United States)

    Zicans, Janis; Meri, Remo Merijs; Ivanova, Tatjana; Berzina, Rita; Saldabola, Ruuta; Maksimov, Robert


    Suitability of recycled acrylonitrile-butadiene-styrene (R-ABS) and recycled polycarbonate (R-PC) for the development of polymer matrix nanocomposites with organically modified nanoclay (OMMT) is evaluated in comparison to virgin polymers (V-ABS and V-PC) based systems. The influence of OMMT content on the structure as well as calorimetric, mechanical and thermal properties of virgin and recycled polymers containing systems is revealed. Increase in stiffness and strength of virgin and recycled polymers based systems is observed along with rising nanoclay content. However, it is observed that reinforcing efficiency of clays on the R-ABS containing systems is reduced to certain extent in comparison to those, based on virgin polymers. It is shown, that in the presence of OMMT approximation of glass transition temperatures of both polymeric components is observed, which can testify about certain improvement of compatibility between PC and ABS. Increment of the modulus of elasticity and yield strength of the nanocomposites is associated with anisodiametric shape of OMMT, as well as with intercalation of polymer within the interlaminar space of the clay nanoparticles. It is also demonstrated that addition of nanoclay improves thermogravimetric behavior of the investigated compositions. Consequently, it is suggested that nanoclays can be used as promising functional additives and replace halogenated flame-retardants, without reducing mechanical properties of the composites.

  7. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg


    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  8. Binary Polymer Brushes of Strongly Immiscible Polymers. (United States)

    Chu, Elza; Babar, Tashnia; Bruist, Michael F; Sidorenko, Alexander


    The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

  9. Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Szymusiak, Magdalena [Department; Kalkowski, Joseph [Department; Luo, Hanying [Department; Donovan, Alexander J. [Department; Zhang, Pin [Department; Liu, Chang [Department; Shang, Weifeng [Department; Irving, Thomas [Department; Herrera-Alonso, Margarita [Department; Liu, Ying [Department; Department


    A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. The structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.

  10. Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying; Donovan, Alexander J.; Zhang, Pin; Liu, Chang; Shang, Weifeng; Irving, Thomas; Herrera-Alonso, Margarita; Liu, Ying (JHU); (IIT); (UIC)


    A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. The structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.

  11. Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

    Directory of Open Access Journals (Sweden)

    Chung Sol Kim


    Full Text Available Triblock copolymers of polystyrene (PS and a polyolefin (PO, e.g., PS-block-poly(ethylene-co-1-butene-block-PS (SEBS, are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH22Zn was prepared, from which poly(ethylene-co-propylene chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta (pmdeta = pentamethyldiethylenetriamine. We found that the fraction of the extracted PS homopolymer was low (~20% and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa. Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

  12. Unidirectional alignment of block copolymer templated porous films using solvent vapor annealing with soft shear (United States)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan


    Porous films templated by block copolymers (BCPs) have been extensively investigated due to their potential numerous applications such as sorbents and nanolithography. However, in many cases, their performance critically depends on their nanostructural alignment and orientation. Achieving unidirectional alignment of these nanostructures over macroscopic dimensions is still challenging especially for BCPs with very high χ and Tg. Here, we illustrate a new method based on solvent vapor annealing with soft shear (SVA-SS), where a crosslinked poly(dimethylsiloxane) (PDMS) cap is simply adhered to the polymer films during SVA, to fabricate macroscopically aligned cylindrical structured mesoporous films using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the soft-template and phenolic resin as the precursor. The evolution of structures through the SVA-SS, thermal annealing and carbonization is determined by grazing incidence small angle x-ray scattering (GISAXS) and atomic force microscopy (AFM). Highly ordered mesoporous carbon films with S>0.8 can be obtained by this method. Potential applicability of this method to nanostructures besides cylinders, such as spheres and gyroid will be discussed.

  13. Influence of Architecture, Concentration, and Thermal History on the Poling of Nonlinear Optical Chromophores in Block Copolymer Domains

    Energy Technology Data Exchange (ETDEWEB)

    Leolukman, Melvina; Paoprasert, Peerasak; Wang, Yao; Makhija, Varun; McGee, David J.; Gopalan, Padma (UW)


    Factors affecting the electric-field-induced poling of nonlinear optical chromophores in block copolymer domains were investigated by encapsulating the chromophores in a linear-diblock copolymer [poly(styrene-b-4-vinylpyridine)] and linear-dendritic (poly(methyl methacrylate)-dendron) block copolymer via hydrogen bonding. Temperature-dependent Fourier transform infrared spectroscopy and morphology evaluation by X-ray scattering and transmission electron microscopy were used with in situ second harmonic generation to correlate domain architectures, processing conditions such as thermal history, and chromophore concentrations with poling efficiency. Poling of chromophores encapsulated in the minority domain (spheres or cylinders) of a linear-diblock copolymer was inhibited by the increasing chromophore concentration within the domain and the chemical nature of the majority domain. Chromophore encapsulation in the majority domain produced the most favorable conditions for poling as measured by in situ second harmonic generation. Thermal annealing of the linear-diblock copolymer/chromophore composites resulted in chromophore aggregation with a corresponding decrease in nonlinear optical activity. The linear-dendron/chromophore system presented the most effective architecture for spatially dispersing chromophores. These findings suggest that while well-ordered phase-separated systems such as block copolymers enhance chromophore isolation over homopolymer systems, a more effective approach is to explore polymer chains end functionalized with chromophores.

  14. Gel polymer electrolytes for batteries (United States)

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


    Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at C.

  15. Simultaneous production of biobased styrene and acrylates using ethenolysis

    NARCIS (Netherlands)

    Spekreijse, J.; Notre, le J.E.L.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.


    Phenylalanine (1), which could be potentially obtained from biofuel waste streams, is a precursor of cinnamic acid (2) that can be converted into two bulk chemicals, styrene (3) and acrylic acid (4), via an atom efficient pathway. With 5 mol% of Hoveyda–Grubbs 2nd generation catalyst, 1 bar of

  16. Graft copolymerization and characterization of styrene with chitosan ...

    African Journals Online (AJOL)

    In this study, styrene was successfully grafted onto chitosan by conventional free radical polymerization technique, using potassium persulphate (KPS) as the initiator. The effect of various reaction conditions including chitosan:monomer weight ratio, polymerization temperature, reaction time and concentration of initiator ...

  17. Terpolymerization of 2-ethoxy ethylmethacrylate, styrene and maleic ...

    Indian Academy of Sciences (India)

    Terpolymerization of 2-ethoxyethyl methacrylate (2-EOEMA), styrene (St) and maleic anhydride (Ma) initiated by benzoyl peroxide was carried out in acetone as common solvent for three monomers. The structure and composition of terpolymer were determined by FTIR spectroscopy by recording analytical absorption bands ...

  18. Occupational Styrene Exposure on Auditory Function Among Adults: A Systematic Review of Selected Workers

    Directory of Open Access Journals (Sweden)

    Francis T. Pleban


    Full Text Available A review study was conducted to examine the adverse effects of styrene, styrene mixtures, or styrene and/or styrene mixtures and noise on the auditory system in humans employed in occupational settings. The search included peer-reviewed articles published in English language involving human volunteers spanning a 25-year period (1990–2015. Studies included peer review journals, case–control studies, and case reports. Animal studies were excluded. An initial search identified 40 studies. After screening for inclusion, 13 studies were retrieved for full journal detail examination and review. As a whole, the results range from no to mild associations between styrene exposure and auditory dysfunction, noting relatively small sample sizes. However, four studies investigating styrene with other organic solvent mixtures and noise suggested combined exposures to both styrene organic solvent mixtures may be more ototoxic than exposure to noise alone. There is little literature examining the effect of styrene on auditory functioning in humans. Nonetheless, findings suggest public health professionals and policy makers should be made aware of the future research needs pertaining to hearing impairment and ototoxicity from styrene. It is recommended that chronic styrene-exposed individuals be routinely evaluated with a comprehensive audiological test battery to detect early signs of auditory dysfunction. Keywords: auditory system, human exposure, ototoxicity, styrene

  19. Survey of volatile substances in kitchen utensils made from acrylonitrile-butadiene-styrene and acrylonitrile-styrene resin in Japan. (United States)

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile-butadiene-styrene resin (ABS) and acrylonitrile-styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectively. The residual levels of 1,3-butadiene ranged from 0.06 to 1.7 μg/g in ABS, and three of 15 ABS samples exceeded the regulatory limit for this compound as established by the European Union (EU). The residual levels of acrylonitrile ranged from 0.15 to 20 μg/g in ABS and from 19 to 180 μg/g in AS. The levels of this substance in seven ABS and six AS samples exceeded the limit set by the U.S. Food and Drug Administration (FDA). Furthermore, the levels of acrylonitrile in three AS samples exceeded the voluntary standard established by Japanese industries. These results clearly indicate that the residual levels of some volatile compounds are still high in ABS and AS kitchen utensils and further observations are needed.

  20. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan (United States)

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin (ABS) and acrylonitrile–styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectively. The residual levels of 1,3-butadiene ranged from 0.06 to 1.7 μg/g in ABS, and three of 15 ABS samples exceeded the regulatory limit for this compound as established by the European Union (EU). The residual levels of acrylonitrile ranged from 0.15 to 20 μg/g in ABS and from 19 to 180 μg/g in AS. The levels of this substance in seven ABS and six AS samples exceeded the limit set by the U.S. Food and Drug Administration (FDA). Furthermore, the levels of acrylonitrile in three AS samples exceeded the voluntary standard established by Japanese industries. These results clearly indicate that the residual levels of some volatile compounds are still high in ABS and AS kitchen utensils and further observations are needed. PMID:24936293

  1. Block Copolymer Adhesion Promoter: Effect of Non Adsorbing Block Length and Substrate Polarity (United States)

    Costa, Ana Claudia; Composto, Russell J.; Vlcek, Petr; Satija, Sushil; Ivkov, Robert


    Block copolymer adsorption to polar substrates is investigated using neutron reflectivity and forward recoil spectrometry. The adhesion promoter is poly (deuterated styrene-block-methylmethacrylate) (dPS-b-MMA) having a short and nearly constant MMA block, which adsorbs to the substrate. The non-adsorbing dPS block length, NdPS, is systematically varied from below to above the entanglement degree of polymerization (Ne). The dPS-b-MMA is blended with a PS matrix, which represents a nearly neutral environment for the dPS block. The substrates are silicon oxide and an organic monolayer of an amino terminated silane. Dewetting studies show that film stability increases as NdPS approaches Ne and as the substrate becomes more hydrophobic. These macroscopic results suggest that entanglements across the matrix/adsorbed layer interface and a strong MMA-substrate interaction can greatly improve thin film stability.

  2. Polymers at liquid-liquid interfaces: Photophysics and photoredox chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Webber, S.E.


    This report consists of three sections: study of triplet state electron transfer from polymer-bound anthracene and pyrene chromophores, adsorption of alternating block and comb polymers onto polymer surfaces, and discussion of transient absorption systems.

  3. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, James E.; Baird, Donald G.


    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  4. Mechanical behavior of styrene grafted PVC films by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Jessica R.; Moura, Eduardo; Somessari, Elisabeth S.R.; Silveira, Carlos G.; Paes, Helio A.; Souza, Carlos A.; Manzoli, Jose E.; Geraldo, Aurea B.C., E-mail:, E-mail: [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)


    The polyvinyl chloride (PVC) is a technological and low cost polymer, however it presents high sensitivity to high energy irradiation because of the weakness of carbon-chloride bond face to carbon-carbon and carbon-hydrogen bonds. Grafting is a type of co-polymerization process that can allow it an increase of mechanical characteristics. The aim of this work is to evaluate the mechanical properties of styrene grafted PVC by electron beam irradiation using mutual and pre-irradiation methods to verify the mechanical resistance changes of obtained product whether grafting process is applied from non-irradiated or from pre-irradiated substrates. The irradiation procedures were performed in atmosphere air or inert atmosphere and the irradiation conditions comprised doses from 10 kGy to 100 kGy and dose rates of 2.2 kGy/s and 22.4 kGy/s. The styrene grafted samples were analyzed by gravimetry to determinate the grafting yield; the final values have been averaged from a series of three measurements. The Mid-A TR-FTIR was the spectrophotometer technique used for qualitative/semi-quantitative analysis of grafted samples. The Young's module and tensile strength of pre-irradiated and grafted PVC samples at both methods were measured at a Lloyd LXR tensile tester at a cross-head speed of 10.00 mm/min. We observed the decrease of Young's module and tensile strength with the increase of absorbed dose at pre-irradiated PVC samples. These mechanical parameters results are discussed. (author)


    Directory of Open Access Journals (Sweden)

    G. V. Popov


    Full Text Available The comparative study of change of surface tension of solutions of some commercial rubbers before and after thermal ageing technique du-Nui, analyzed the features of change of surface tension of solutions of various rubbers in the presence of a mixture of fullerenes. Calculations of the Gibbs energy and the analysis of the obtained data to predict the behavior of polymer systems when changes are made to mix of fullerenes in a wide concentration range. When comparing the results of changes in Gibbs energy and the surface tension in fluids rubbers shown that mentioned above in solutions of elastomers aged, than the control. This fact confirms the initial chapeau of physic-chemical interactions of molecules fullerenes by segments of the Kuna and end groups of the polymer chains, as it is known that when thermal-oxidative degradation of rubbers, respectively the number of segments of the Kuna and branched loose ends of macromolecules that are free to react with fullerenes in solution, free from spatial constraints. A comparative analysis of the interaction of rubbers with different chemical composition with double branches has shown that it is easier to just react and has minimum energy polibutadien interaction that has to do with lack of branching and no radicals in its structure and in the backbone chain. The maximum energy of interaction with Fullerenes have SBS rubber because it has large styrene blocks in the main polymer chain that causes the spatial constraints to direct contact with fullerene molecules, you can assume that the interaction is only low-molecular fraction of Fullerenes mixture, possessing the necessary dimensions. As a result of the study shows that the application of the method of separation ring (Du-Nui allows you to predict the properties of rubber with modified nanomaterial’s with minimal labor costs.


    Directory of Open Access Journals (Sweden)


    Full Text Available Asphalt is one of the most commonly used building material. The first attempts at modifying asphalt were made at the beginning of the twentieth century. Nowadays the most popular asphalt modifier is the styrene-butadiene-styrene (SBS. This thermoplastic elastomer increases the thermal resistance of bitumen, widens the range of plasticity and amends rheological properties. IR spectroscopy is by far the most common instrumental method used in analytical chemistry. The popularity of this method results from its simple measurement technique, universality and high precision. That is why IR spectroscopy applies to the analysis of polymer modified binder (PMB used in waterproofing.

  7. Removal of styrene from waste gas stream using a biofilter

    Directory of Open Access Journals (Sweden)

    B Bina


    Full Text Available Background: Styrene is produced in large quantities in the chemical industries and it has been listed among the 189 hazardous and toxic atmospheric contaminants under Clean Air Act Amendments, 1990, due to its adverse effects on human health. The biofiltration has been widely and efficiently applied during recent decades for the treatment of air streams contaminated by volatile organic compounds at low concentrations. Also this technology has been applied widely and efficiently in the removal of styrene from waste gas streams. Methods: Biofiltration of waste gas stream polluted by styrene vapor was investigated in a three-stage bench scale reactor. Yard waste compost using shredded hard plastics as a bulking agent in a 75:25 v/v mix of plastics:compost was used to packing biofilter. The system inoculation was achieved by adding thickened activated sludge obtained from municipal wastewater treatment plant and the effects of loading rate, inlet concentration, and empty bed retention time variations on the performance and operation of biofilter were studied. Results: Microbial acclimation to styrene was achieved with inlet concentration of 65 ± 11 ppm and bed contact time of 360 s after 57 days of operation. Under steady state conditions experimental results showed equal average removal efficiency of about 84% at loading rates of 60 and 80 g m-3 h-1 with empty bed retention time of 60 s. Maximum elimination capacity was obtained up to 81 g m-3 h-1 with organic loading rate of about 120 g m-3 h-1. Reduction in performance was observed at inlet concentrations of upper than 650 ppm related to organic loading rates up to 160 g m-3 h-1 and then removal efficiency was decreased sharply. Evaluation of the concentration profile along the bed height of column indicated that the most value of elimination capacity occurred in the first section of biofilter. Elimination capacity also showed higher performance when empty bed retention time was reduced to 30 s

  8. Recycling cycle of materials applied to acrylonitrile-butadiene-styrene/policarbonate blends with styrene-butadiene-styrene copolymer addition (United States)

    Cândido, L. H. A.; Ferreira, D. B.; Júnior, W. Kindlein; Demori, R.; Mauler, R. S.


    The scope of this research is the recycling of polymers from mobile phones hulls discarded and the performance evaluation when they are submitted to the Recycling Cycle of Materials (RCM). The studied material was the ABS/PC blend in a 70/30 proportion. Different compositions were evaluated adding virgin material, recycled material and using the copolymer SBS as impact modifier. In order to evaluate the properties of material's composition, the samples were characterized by TGA, FTIR, SEM, IZOD impact strength and tensile strength tests. At the first stage, the presented results suggest the composition containing 25% of recycled material and 5% of SBS combines good mechanical performance to the higher content of recycled material and lower content of impact modifier providing major benefits to recycling plans. Five cycles (RCM) were applied in the second stage; they evidenced a decrease trend considering the impact strength. At first and second cycle the impact strength was higher than reference material (ABS/PC blend) and from the fourth cycle it was lower. The superiority impact strength in the first and second cycles can be attributed to impact modifier effect. The thermal tests and the spectrometry didn't show the presence of degradation process in the material and the TGA curves demonstrated the process stability. The impact surface of each sample was observed at SEM. The microstructures are not homogeneous presenting voids and lamellar appearance, although the outer surface presents no defects, demonstrating good moldability. The present work aims to assess the life cycle of the material from the successive recycling processes.

  9. Thiophene-S,S-dioxidized Indophenine: A Quinoid-Type Building Block with High Electron Affinity for Constructing n-Type Polymer Semiconductors with Narrow Band Gaps. (United States)

    Deng, Yunfeng; Sun, Bin; He, Yinghui; Quinn, Jesse; Guo, Chang; Li, Yuning


    Three thiophene-S,S-dioxidized indophenine (IDTO) isomers, 3 a (E,E,E), 3 b (Z,E,E), and 3 c (Z,E,Z), were synthesized by oxidation of an indophenine compound. 3 b and 3 c could be converted into the most-stable 3 a by heating at 110 °C. An IDTO-containing conjugated polymer, PIDTOTT, was prepared using 3 a as a comonomer through a Stille coupling reaction, and it possesses a narrow band gap and low energy levels. In organic field effect transistors (OFETs), PIDTOTT exhibited unipolar n-type semiconductor characteristics with unexpectedly high electron mobility (up to 0.14 cm(2)  V(-1)  s(-1)), despite its rather disordered chain packing. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Styren a styren-7,8-oxid:metabolismus a analytické metody stanovení aduktů s proteiny

    Czech Academy of Sciences Publication Activity Database

    Jágr, Michal; Pacáková, V.; Petříček, Miroslav


    Roč. 103, č. 11 (2009), s. 902-910 ISSN 0009-2770 Institutional research plan: CEZ:AV0Z50200510 Keywords : styren * adducts * styren-7,8-oxid Subject RIV: EE - Microbiology, Virology Impact factor: 0.717, year: 2009

  11. 1D coordination polymers formed by tetranuclear lead(II) building blocks with carboxylate ligands: In situ isomerization of itaconic acid

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Abhinandan; Jana, Swapan Kumar; Datta, Sayanti [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India); Butcher, Raymond J. [Department of Chemistry, Howard University, Washington, DC (United States); Zangrando, Ennio [Department of Chemical and Pharmaceutical Sciences, University of Trieste, 34127 Trieste (Italy); Dalai, Sudipta, E-mail: [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal (India)


    The synthesis of two new lead(II) coordination polymers, [Pb{sub 2}(mpic){sub 4}(H{sub 2}O)]·0.5H{sub 2}O (1) and [Pb{sub 2}(phen){sub 2}(cit)(mes)]·2H{sub 2}O (2) has been reported, where mpic=3-methyl picolinate, phen=o-phenanthroline, H{sub 2}cit=citraconic acid, H{sub 2}mes mesaconic acid. X-ray single crystal diffraction analyses showed that the complexes comprise topologically different 1D polymeric chains stabilized by weak interactions and both containing tetranuclear Pb{sub 4} units connected by carboxylate groups. In compound 1 3-methylpicolinic acid is formed in situ from 3-methyl piconitrile, and mesaconate and citraconate anions were surprisingly formed from itaconic acid during the synthesis of 2. The photoluminescence and thermal properties of the complexes have been studied. - Graphical abstract: Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by X-ray analysis. The luminescence and thermal properties have been studied. Display Omitted - Highlights: • Both the complexes, made up of different ligands, forms topologycally different 1D polymeric chains containing Pb{sub 4} clusters. • The final structures are stabilized by weak interactions (H-bond, π∙∙∙π stacking). • In complex 1, the 3-methylpicolinic acid is generated in situ from 3-methyl piconitrile. • Mesaconate and citraconate anions are surprisingly formed in situ from itaconic acid during the synthesis of complex 2, indicating an exceptional transformation.

  12. Oleylamine-functionalized graphene oxide as an electron block layer towards high-performance and photostable fullerene-free polymer solar cells. (United States)

    Liu, Zhiyong; Niu, Shengli; Wang, Ning


    Oleylamine-functionalized graphene oxide (GO) has a shallower energy level of conduction band (ECB) and a deeper energy level of the valence band (EVB) as compared to common hole extraction layer (HEL) materials, which make the electron block layer (EBL). Photoluminescence, X-ray photoelectron spectroscopy (XPS), and current density-voltage (J-V) curves with a large reverse bias voltage range obtained under dark conditions are used to determine whether GO layers play important roles in blocking the electron transport to the MoO3/Ag composite anode and prevent MoO3 diffusion into a photoactive layer under light illumination. Moreover, GO inserted between a photoactive layer and an HEL enhances charge carrier transport and collection and avoids the monomolecular recombination between the photoactive layer and HEL. Photovoltaic parameters and photostability measurements of inverted and forward PSCs have shown that upon introduction of GO, the performance and photostability of PSCs are improved. On adding GO to PSCs, the power conversion efficiency (PCE) increases approximately 5% and 4% and reduces the decay ratio to approximately 50% and 65% of the initial value for the inverted and forward PSCs, respectively.

  13. Population Blocks. (United States)

    Smith, Martin H.


    Describes an educational game called "Population Blocks" that is designed to illustrate the concept of exponential growth of the human population and some potential effects of overpopulation. The game material consists of wooden blocks; 18 blocks are painted green (representing land), 7 are painted blue (representing water); and the remaining…

  14. Compatibility, Morphology, Mechanical Properties and Biodegradability of Poly(styrene-ethylene-propylenestyrene/ Modified Thermoplastic Starch Blends

    Directory of Open Access Journals (Sweden)

    Saaid Rahimi Bandarabadi


    Full Text Available The effect of modified starch on the properties of poly(styrene-ethylenepropylene- styrene tri-block copolymer was studied. Chemical treatment of starch with maleic anhydride was accomplished in an internal mixer in the presence of glycerol. The reaction was confirmed using Fourier infrared spectroscopy (FTIR and titration. The blend samples containing 10, 20, 30 and 50 wt% were obtained by melt blending and their mechanical, morphological and dynamic-mechanical properties were studied. Scanning electron microscopy (SEM images displayed droplet-matrix morphology and with increases in modified starch up to 50 wt% some partial co-continuous morphology was also observed. With increase of modified starch in the compound, the size of dispersed phase increased. DMTA results revealed that the partial compatibility was obtained because of slight difference between glass transition temperatures of two phases in the presence of modified starch. The peak of modified starch shifted to higher values and the differences between the two peaks decreased, indicating partial compatibility. Mechanical properties including tensile, elongation-at-break and modulus were also determined and the results showed that the mechanical properties of the sample were higher than those of neat TPS because of the higher compatibility. Tensile strength was decreased with increase in modified starch content due to the absence of strong interfacial adhesion. Moduli of the samples were increased with increase in modified starch content due to higher stiffness of starch. Biodegradability of the samples was evaluated by weight loss percentage using compost test. A rapid degradation was observed in the first 45 days and with increase of the modified starch content the degree of degradation was increased.

  15. Fall From High and Acute Styrene Exposure : A Case Report

    Directory of Open Access Journals (Sweden)

    Ferhat Ižcme


    Full Text Available Styrene is a benzene derivative of the aromatic hydrocarbon which is widely used in the manufacture of plastics industry, synthetic rubber and insulating materials. Its toxic effects occur by inhalation of its vapor or by direct contact. In acute intoxication irritation in the eye and skin may occur and chemical pneumonitis may develop in the lungs due to inhalation. It dissolves in ethanol, benzene, acetone and ether. Water solubility is low. In this paper we present the management of a patient who after falling down from the scaffold which is approximately 5 meters of height, a tin of styrene on the same scaffold spilled on him and we would like to draw attention to the need for decontamination chamber which is not available in the most of the emergency departments in our country.

  16. Acute behavioral effects of styrene exposure: a further analysis

    Energy Technology Data Exchange (ETDEWEB)

    Cherry, N.; Rodgers, B.; Venables, H.; Waldron, H.A.; Wells, G.G.


    Studies were carried out on two groups to styrene-based resin. Early morning urinary mandelic acid concentrations after two days without exposure correlated with reaction time measured on arrival at work. Men were found to differ considerably in their rate of clearance of mandelic acid-those with slow reaction times. After some months at reduced exposure, a small group of men with previously high mandelic acid concentrations has speeded up on the reaction time task.

  17. Magnetic Field Alignment of PS-P4VP: a Non-Liquid Crystalline Coil-Coil Block Copolymer (United States)

    Rokhlenko, Yekaterina; Zhang, Kai; Larson, Steven; Gopalan, Padma; O'Hern, Corey; Osuji, Chinedum


    Magnetic fields provide the ability to control alignment of self-assembled soft materials such as block copolymers. Most prior work in this area has relied on the presence of ordered assemblies of anisotropic liquid crystalline species to ensure sufficient magnetic anisotropy to drive alignment. Recent experiments with poly(styrene-b-4-vinylpyridine), a non-liquid crystalline BCP, however, show field-induced alignment of a lamellar microstructure during cooling across the order-disorder transition. Using in situ x-ray scattering, we examine the roles of field strength and cooling rate on the alignment response of this low MW coil-coil BCP. Alignment is first observed at field strengths as low as 1 Tesla and improves markedly with both increasing field strength and slower cooling. We present a geometric argument to illustrate the origin of a finite, non-trivial magnetic susceptibility anisotropy for highly stretched surface-tethered polymer chains and corroborate this using coarse-grained molecular dynamics simulations. We rationalize the magnetic field response of the system in terms of the mobility afforded by the absence of entanglements, the intrinsic anisotropy resulting from the stretched polymer chains and sterically constrained conjugated rings, and the large grain size in these low molecular weight materials.

  18. Extending Long-lived Charge Separation Between Donor and Acceptor Blocks in Novel Copolymer Architectures Featuring a Sensitizer Core. (United States)

    Schroot, Robert; Schlotthauer, Tina; Dietzek, Benjamin; Jäger, Michael; Schubert, Ulrich S


    A bifunctional RuII photosensitizer unit was decorated with one n- and one p-type polymer chain to form precisely controlled hierarchical copolymer-type architectures for light-induced charge separation. The applied modular chemistry-on-the-complex strategy benefits from separately prepared building blocks and their orthogonal linkage in the two final assembly steps. Upon visible light absorption, electron transfer is initiated between the conjugated poly(3,6-carbazole) chain and the styrenic poly(naphthalene diimide) segments. Steady-state and time-resolved spectroscopy show complete charge separation within a few nanoseconds (>95 % efficiency) persisting several tens of microseconds. The recombination is significantly reduced in comparison to low-molecular model systems or to non-conjugated congeners, reflecting the higher charge mobility in conjugated polymers. In summary, the modularity of the presented approach is expected to serve as a versatile platform to tailor the interface between the charge transport domains in a systematic fashion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Confined space hazards: combined exposure to styrene, fiberglass, and silica. (United States)

    Shields, P G; McCunney, R J; Chase, K H


    Work in confined spaces continues to present hazards to workers. The magnitude of this problem was recently addressed by the Occupational Safety and Health Administration in its Final Rule for "Permit-Required Control Spaces for General Industry" (29 CFR Parts 1910). Although illness and injury are typically due to asphyxiation, explosion, and drowning, toxic exposures also are an important risk. We describe herein four workers engaged in erosion-proofing enclosed chemical tanks with minimal ventilation and no respiratory protection. They were exposed to styrene-based solvents, styrene-based resins, silica, and fiberglass dust. Each experienced acute neurological effects and bronchitis. One worker developed a life-threatening pneumonia that resulted in numerous complications. The severity of the illness, which would likely not have otherwise occurred, resulted from impaired lung defense mechanisms due to the combined exposures. Several studies support the association of styrene exposure and respiratory illness that may be compounded by co-exposure to fiberglass in unique circumstances. To prevent the hazards of confined space, recommended procedures should be followed, including those established by the National Institute for Occupational Safety and Health and the Occupational Safety and Health Administration.

  20. Styrene biofiltration in a trickle-bed reactor

    Directory of Open Access Journals (Sweden)

    V. Novak


    Full Text Available The biological treatment of styrene waste gas in a trickle-bed filter (TBF was investigated. The bioreactor consisted of a two-part glass cylinder (ID 150 mm filled with 25 mm polypropylene Pall rings serving as packing material. The bed height was 1m. Although the laboratory temperature was maintained at 22 ºC, the water temperature in the trickle-bed filter was slightly lower (about 18 ºC.The main aim of our study was to observe the effect of empty-bed residence time (EBRT on bioreactor performance at a constant pollutant concentration over an extended time period. The bioreactor was inoculated with a mixed microbial consortium isolated from a styrene-degrading biofilter that had been running for the previous two years. After three weeks of acclimation period, the bioreactor was loaded with styrene (100 mg.m-3. EBRT was in the range of 53 s to 13 s. A maximum elimination capacity (EC of 11.3 gC.m-3.h-1 was reached at an organic loading (OL rate of 18.6 gC.m-3.h-1.

  1. AFM study of excimer laser patterning of block-copolymer: Creation of ordered hierarchical, hybrid, or recessed structures

    Energy Technology Data Exchange (ETDEWEB)

    Švanda, Jan; Siegel, Jakub; Švorčík, Vaclav; Lyutakov, Oleksiy, E-mail:


    Highlights: • Combination of bottom-up (BCP separation) and top-down (laser patterning) technologies allows obtaining hierarchical structures. • Surface morphologies were determined by the order of patterning steps (laser modification, annealing, surface reconstruction). • Tuning the order of steps enables the reorientation of BCP domain at large scale, fabrication of hierarchical, hybrid or recessed structures. • The obtained structures can find potential applications in nanotechnology, plasmonics, information storage, sensors and smart surfaces. - Abstract: We report fabrication of the varied range of hierarchical structures by combining bottom-up self-assembly of block copolymer poly(styrene-block-vinylpyridine) (PS-b-P4VP) with top-down excimer laser patterning method. Different procedures were tested, where laser treatment was applied before phase separation and after phase separation or phase separation and surface reconstruction. Laser treatment was performed using either polarized laser light with the aim to create periodical pattern on polymer surface or non-polarized light for preferential removing of polystyrene (PS) part from PS-b-P4VP. Additionally, dye was introduced into one part of block copolymer (P4VP) with the aim to modify its response to laser light. Resulting structures were analyzed by XPS, UV–vis and AFM techniques. Application of polarized laser light leads to creation of structures with hierarchical, recessed or hybrid geometries. Non-polarized laser beam allows pronouncing the block copolymer phase separated structure. Tuning the order of steps or individual step conditions enables the efficient reorientation of block-copolymer domain at large scale, fabrication of hierarchical, hybrid or recessed structures. The obtained structures can find potential applications in nanotechnology, photonics, plasmonics, information storage, optical devices, sensors and smart surfaces.

  2. Perforated layer structures in liquid crystalline block copolymers (United States)

    Tenneti, Kishore; Chen, Xiaofang; Li, Christopher; Tu, Yingfeng; Wan, Xinhua; Zhou, Qi-Feng; Sics, Igors; Hsiao, Benjamin


    Phase structures of a series of poly(styrene-block-(2,5-bis-(4- methoxyphenyl)oxycarbonyl)styrene) (PS-b-PMPCS) liquid crystalline “rod-coil” block copolymers (LCBCPs) were investigated using thermal analysis, X-ray analysis and transmission electron microscopy. In the low molecular weight asymmetric BCP system, perforated layer structures were observed where the excessive PS molecules punctured the PMPCS domains and these perforations uniquely possess tetragonal in- plane symmetry. In the high molecular weight system, these perforated layer structures were observed in symmetric samples. Randomly initiated perforations became more regular and uniform upon blending with PS homopolymer in symmetric BCPs. These regular perforations also possess tetragonal in-plane symmetry.

  3. Concentration Dependent Structure of Block Copolymer Solutions (United States)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.


    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  4. Chromosomal aberrations in lymphocytes of workers exposed to low levels of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Nordenson, I.; Beckman, L.


    Chromosomal aberrations were studied in lymphocytes of 15 workers exposed to styrene and 13 controls. The average styrene concentration in the work room air was 24 ppm, and the levels of urinary mandelic acid were below 2 mmol/l. No significant increase in the rates of gaps and breaks was found. However, the rate of micronuclei was significantly increased, which indicates that the mitotic spindle mechanism may be more sensitive to styrene and its metabolites than DNA.

  5. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars


    A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  6. Light emission in quantum dots and dyes doped polymer nanofibers (United States)

    Li, Baojun; Cheng, Chang; Yang, Xianguang


    Polymer nanofibers are cheap and flexible building blocks for nanophotonic components. For high density nanophotonic integration, both passive and active polymer nanofibers are desirable. In contrast to passive polymer nanofibers, active polymer nanofibers are more desirable because they can act as a light source and waveguide simultaneously. In this talk, light emission in quantum dots and dyes doped polymer nanofibers will be introduced.

  7. Thermal Stability and Flammability of Styrene-Butadiene Rubber-Based (SBR) Ceramifiable Composites

    National Research Council Canada - National Science Library

    Anyszka, Rafał; Bieliński, Dariusz; Pędzich, Zbigniew; Rybiński, Przemysław; Imiela, Mateusz; Siciński, Mariusz; Zarzecka-Napierała, Magdalena; Gozdek, Tomasz; Rutkowski, Paweł


    Ceramifiable styrene-butadiene (SBR)-based composites containing low-softening-point-temperature glassy frit promoting ceramification, precipitated silica, one of four thermally stable refractory fillers...

  8. Fabrication and actuation of electro-active polymer actuator based on PSMI-incorporated PVDF (United States)

    Lu, Jun; Kim, Sang-Gyun; Lee, Sunwoo; Oh, Il-Kwon


    In this study, an ionic networking membrane (INM) of poly(styrene-alt-maleimide) (PSMI)-incorporated poly(vinylidene fluoride) (PVDF) was applied to fabricate electro-active polymer. Based on the same original membrane of PSMI-incorporated PVDF, various samples of INM actuator were prepared for different reduction times with the electroless-plating technique. The as-prepared INM actuators were tested in terms of surface resistance, platinum morphology, resonance frequency, tip displacement, current and blocked force, and their performances were compared to those of the widely used traditional Nafion actuator. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that much smaller and more uniform platinum particles were formed on the surfaces of the INM actuators as well as within their polymer matrix. Although excellent harmonic responses were observed for the newly developed INM actuators, they were found to be sensitive to the applied reduction times during the fabrication. The mechanical displacement of the INM actuator fabricated after the optimum reduction times was much larger than that of its Nafion counterpart of comparable thickness under the stimulus of constant and alternating current voltage. The PSMI-incorporated PVDF actuator can become a promising smart material to be used in the fields of biomimetic robots, biomedical devices, sensors and actuator, haptic interfaces, energy harvesting and so on.

  9. The effect of heat treatment on the internal structure of nanostructured block copolymer films

    DEFF Research Database (Denmark)

    Sepe, Alessandro; Hoppe, E T; Jaksch, S


    We report on the temperature dependence of the nanostructure of thin block copolymer films, as studied using in situ grazing-incidence small-angle x-ray scattering (GISAXS). We focus on spin-coated poly(styrene-b-butadiene) diblock copolymer thin films featuring lamellae perpendicular to the subs...

  10. Optimization of electrochemical and peroxide-driven oxidation of styrene with ultrathin polyion films containing cytochrome P450cam and myoglobin. (United States)

    Munge, Bernard; Estavillo, Carmelita; Schenkman, John B; Rusling, James F


    The catalytic and electrochemical properties of myoglobin and cytochrome P450(cam) in films constructed with alternate polyion layers were optimized with respect to film thickness, polyion type, and pH. Electrochemical and hydrogen peroxide driven epoxidation of styrene catalyzed by the proteins was used as the test reaction. Ionic synthetic organic polymers such as poly(styrene sulfonate), as opposed to SiO(2) nanoparticles or DNA, supported the best catalytic and electrochemical performance. Charge transport involving the iron heme proteins was achieved over 40-320 nm depending on the polyion material and is likely to involve electron hopping facilitated by extensive interlayer mixing. However, very thin films (ca. 12-25 nm) gave the largest turnover rates for the catalytic epoxidation of styrene, and thicker films were subject to reactant transport limitations. Classical bell-shaped activity/pH profiles and turnover rates similar to those obtained in solution suggest that films grown layer-by-layer are applicable to turnover rate studies of enzymes for organic oxidations. Major advantages include enhanced enzyme stability and the tiny amount of protein required.

  11. Radical polymerization of styrene controlled by half-sandwich Mo(III)/Mo(IV) couples: all basic mechanisms are possible. (United States)

    Le Grognec, E; Claverie, J; Poli, R


    Density functional calculations of bond dissociation energies (BDEs) have been used as a guide to the choice of metal system suitable for controlling styrene polymerization by either the stable free radical polymerization (SFRP) or the atom transfer radical polymerization (ATRP) mechanism. In accord with the theoretical prediction, CpMo(eta(4)-C(4)H(6))(CH(2)SiMe(3))(2), 2, is not capable of yielding SFRP of styrene. Still in accord with theoretical prediction, CpMo(eta(4)-C(4)H(6))Cl(2), 1, CpMo(PMe(3))(2)Cl(2), 3, and CpMo(dppe)Cl(2) (dppe = 1,2-bis(diphenylphosphino)ethane), 4, yield controlled styrene polymerization by the SFRP mechanism in the presence of 2,2'-azobisisobutyronitrile (AIBN). This arises from the generation of a putative Mo(IV) alkyl species from the AIBN-generated radical addition to the Mo(III) compound. The controlled nature of the polymerizations is indicated by linear M(n) progression with the conversion in all cases and moderate polydispersity indices (PDIs). Controlled polymerization of styrene is also given by compounds 3 and 4 in combination with alkyl bromides. These complexes then operate by the ATRP mechanism, again in accord with the theoretical predictions. Controlled character is revealed by linear increase of M(n) versus conversion, low PDIs, a stop-and-go experiment, and (1)H NMR and MALDI-TOF analyses of the polymer end groups. The same controlled polymerization is given by a "reverse" ATRP experiment, starting from AIBN and CpMo(PMe(3))(2)Cl(2)Br, 5. On the other hand, when compound 1 or 2 is used in combination with an alkyl bromide (as for an ATRP experiment), the isolated polystyrene shows by M(n), (1)H NMR, and MALDI-TOF analyses that catalytic chain transfer (CCT) radical polymerization takes place in this case. Kinetics simulations underscore the conditions regulating the radical polymerization mechanism and the living character of the polymerization. The complexes herein described are ineffective at controlling the

  12. Mechanisms of Polymer-Templated Nanoparticle Synthesis: Contrasting ZnS and Au. (United States)

    Podhorska, Lucia; Delcassian, Derfogail; Goode, Angela E; Agyei, Michael; McComb, David W; Ryan, Mary P; Dunlop, Iain E


    We combine solution small-angle X-ray scattering (SAXS) and high-resolution analytical transmission electron microscopy (ATEM) to gain a full mechanistic understanding of substructure formation in nanoparticles templated by block copolymer reverse micelles, specifically poly(styrene)-block-poly(2-vinylpyridine). We report a novel substructure for micelle-templated ZnS nanoparticles, in which small crystallites (∼4 nm) exist within a larger (∼20 nm) amorphous organic-inorganic hybrid matrix. The formation of this complex structure is explained via SAXS measurements that characterize in situ for the first time the intermediate state of the metal-loaded micelle core: Zn(2+) ions are distributed throughout the micelle core, which solidifies as a unit on sulfidation. The nanoparticle size is thus determined by the radius of the metal-loaded core, rather than the quantity of available metal ions. This mechanism leads to particle size counterintuitively decreasing with increasing metal content, based on the modified interactions of the metal-complexed monomers in direct contrast to gold nanoparticles templated by the same polymer.

  13. Nitroxide mediated and atom transfer radical graft polymerization of atactic polymers onto syndiotactic polystyrene

    Directory of Open Access Journals (Sweden)

    M. Abbasian


    Full Text Available 'Living' radical graft polymerization was employed to prepare graft copolymers with nitroxide-mediated arylated syndiotactic polystyrene as the backbone and polystyrene (PS, poly(p-methylstyrene (PMS and poly(methylmethacrylate (PMMA as branches. A two-stage process has been developed to synthesize the macroinitiator. First, syndiotactic polystyrene (sPS was modified by the Friedel-Crafts reaction to introduce chlorine; second, the chlorine groups were converted to nitroxide mediated groups by coupling with 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH. The resulting macroinitiator (sPS-TEMPO for 'living' free radical polymerization was then heated in the presence of styrene and p-methylstyrene to form graft and block copolymers. We used the obtained copolymer and N-bromosuccinimide as brominating agent to achieve polymers with bromine groups. This brominated copolymer was used as a macroinitiator for polymerizing methyl methacrylate in the presence of the CuBr/bpy catalyst system. The formation of the graft and block copolymers was confirmed by DSC, ¹H NMR and FTIR spectroscopy. This approach using macroinitiators is an effective method for the preparation of new materials.

  14. Electrically conductive poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)/polyacrylonitrile fabrics for humidity sensors

    Energy Technology Data Exchange (ETDEWEB)

    Panapoy, Manop; Singsang, Witawat; Ksapabutr, Bussarin, E-mail:, E-mail: [Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University, Nakhon Pathom 73000 (Thailand)


    Humidity sensors based on poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS)/polyacrylonitrile (PAN) nanofiber fabric were fabricated by a dip coating of nonwoven PAN nanofiber mat, which was prepared via an electrospinning method, in PEDOT-PSS solution. The influence of PAN solution concentration on their responsiveness to humidity on dynamic testing was monitored as the device was exposed to humidity. With the relative humidity (RH) changing from 0 to 100%, a resistance device response over 110% was achieved, and the curve of the resistance response with RH is of high linearity at the humidity working range of 0-100% RH. The high device reproducibility was demonstrated by carrying out vapor adsorption-desorption dynamic cycles, and the response and recovery times were determined to be of the order of 2-46 and 7-34 s, respectively. These hybrid polymer sensors can be used as disposable handheld instruments due to low cost and light weight.

  15. Organic Semiconducting Materials in Film and Powder Forms from a Co-polymeric Elastomer-Styrene Butadiene Rubber (United States)

    Santhamma, G.; Predeep, P.


    Semiconducting materials in both film and powder forms are prepared by Antimony Pentachloride (SBCl5) doping in Styrene Butadiene Rubber (SBR). SBR is a synthetic co-polymeric elastomer, insulating in undoped state, is mainly used for manufacturing tires, tubes etc. Synthesized conducting materials are proposed to have tremendous application potentials in optoelectronic, electronic and electrical industries. For example conducting films can be used as active elements for fabrication of organic light emitting diodes, photovoltaic cells etc. Electrical and optical properties of prepared samples are studied by measuring electrical conductivity and analyzing spectroscopic data. Electrical conductivity of samples lies in the range of that of semi-conducting materials. Presence of conjugated sequences in the back bone of prepared conducting materials, which is regarded as pre-requisite condition for a polymer to conductive, is confirmed by studying UV/Vis spectra.

  16. Grafting amino drugs to poly(styrene-alt-maleic anhydride) as a potential method for drug release

    Energy Technology Data Exchange (ETDEWEB)

    Khazaei, Ardeshir; Saednia, Shahnaz; Saien, Javad; Abbasi, Fatemeh, E-mail:, E-mail: [Faculty of Chemistry, Bu-Ali Sina University, Hamedan (Iran, Islamic Republic of); Kazem-Rostami, Masoud [Young Researchers Club and Elite, Takestan Branch, Islamic Azad University, Takestan (Iran, Islamic Republic of); Sadeghpour, Mahdieh [Department of Chemistry, Takestan Branch, Islamic Azad University, Takestan (Iran, Islamic Republic of); Borazjani, Maryam Kiani [Faculty of Science, Department of Chemistry, Bushehr Payame Noor University (PNU), Bushehr (Iran, Islamic Republic of)


    Drug delivery systems based on polymer-drug conjugates give an improved treatment with lower toxicity or side effects and be used for the treatment of different diseases. Conjugates of biodegradable poly(styrene-alt-maleic anhydride) (PSMA), with a therapeutic agents such as amantadine hydrochloride, amlodipine, gabapentin, zonisamide and mesalamine, were afforded by the formation of the amide bonds of the amino drugs that reacted with the PSMA anhydride groups. The amounts of covalently conjugated drugs were determined by a {sup 1}H NMR spectroscopic method, and the in vitro release rate in buffer solution (pH 1.3) was studied at body temperature 37 Degree-Sign C. In kinetic studies, different dissolution models were examined to obtain drug release data and the collected data were well-fitted to the Korsmeyer-Peppas equation, revealing a dominant Fickian diffusion mechanism for drug release under the in vitro conditions. (author)

  17. [Determination of lead, cadmium, mercury, chromium and arsenic in acrylonitrile-butadiene-styrene copolymer using microwave digestion-ICP-MS]. (United States)

    Wang, Ying-Feng; Shi, Yan-Zhi; Zhang, Hua; Chen, Yu-Hong; Lau, John; Wilbur, Steven; Li, Ping


    A method was studied for the analysis of Cr, As, Cd, Hg and Pb in acrylonitrile-butadiene-styrene copolymer by using ICP-MS. The instrument parameters were optimized and the introduction system was developed systematically. The sample is decomposed by microwave digestion. The digestion condition was optimized concerning digestion system, proportion of acids and digestion procedure, which affords reference for the preparation of the same kinds of polymer samples. The detection limits of the method for all sample elements were 0.7-6.5 ng x g(-1), the recoveries were 89.8%-110.8%, and the RSDs were 2.8%-11.3%. The analytical method presented was characterized with good precision and accuracy, simplicity, rapidness, low limits of detection and no matrix matching requirements.

  18. Synthesis and characterization of polymer electrolyte membranes with controlled ion transport properties (United States)

    Xu, Kui


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

  19. Monte Carlo, small angle light scattering, and dynamic light scattering studies of dilute polymer solutions (United States)

    McNamara, Joseph E.

    The adsorption of negatively charged polymer, negative/neutral block copolymer and a polyampholyte to patterned surfaces is investigated using off-lattice Monte Carlo simulations. The surface is decorated by stripe and checkerboard patterns of mixed charges. The polymer has periodic charge segments, which potentially match the periodicity of the surface pattern. Results show that the chain entropy of a flexible polymer disrupts and prevents full pattern recognition. Quantities such as average adsorption energy and the radii of gyration of the adsorbed polymer are calculated and found to be dictated by the size of the surface pattern and its correlation to the polymer charge density. We performed small angle light scattering on dilute-solution-grown polyethylene crystals grown from quenches in para-xylene. The quench depths ranged from 60 to 85°C for 0.05 wt.% and 0.1 wt.% linear-low-polydispersity polyethylenes. We found asymmetric scattering patterns for the lower temperature quenches to 65°C, and symmetric scattering patterns for the higher temperature quenches to 80°C. There is a smooth transition from asymmetric to symmetric scattering as we change the quench depth. The correlation lengths d=2pi/qmax corresponding to the peaks of intensity versus q ranged from 15 to 30 mum. We find evidence that these length scales correspond to assemblies of single polyethylene crystals. Also, we have performed dynamic light scattering on solutions of sodium-poly(styrene-sulfonate) (NaPSS) and poly(ethylene-oxide) (PEO) in water with BaCl2. The fast mode ( Dfast) and slow mode (Dslow) diffusion coefficients were measured as a function of polymer concentration for both polymers in dilute solution. We found that the diffusion coefficients remained relatively constant in the concentration regimes investigated and Dfast and Dslow for both polymers differed by about 1½ orders of magnitude: 1.1 x 10-6 cm2/s versus 7.8 x 10-8 cm2/s for NaPSS and 6.7 x 10-7 cm2/s versus 4.2 x 10

  20. Polymer films (United States)

    Granick, Steve; Sukhishvili, Svetlana A.


    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  1. Mechanical and Thermal Properties of Styrene Butadiene Rubber - Functionalized Carbon Nanotubes Nanocomposites

    KAUST Repository

    Laoui, Tahar


    The effect of reinforcing styrene butadiene rubber (SBR) with functionalized carbon nanotubes on the mechanical and thermal properties of the nanocomposite was investigated. Multi-walled carbon nanotubes (CNTs) were functionalized with phenol functional group to enhance their dispersion in SBR matrix. Surface functionalization of the CNTs was carried out using acid treatment and FTIR technique was utilized so as to ascertain the presence of phenol functional group. This was followed with the dispersion of the functionalized CNTs into a polymer solution and a subsequent evaporation of the solvent. This study has demonstrated the inherent capability of CNTs as reinforcing filler as demonstrated by the substantial improvement in Young\\'s Modulus, tensile strength and energy of absorption of the nanocomposites. The tensile strength increased from 0.17 MPa (SBR) to 0.48 MPa while the Young\\'s Modulus increased from 0.25 MPa to 0.83 MPa when 10wt% functionalized CNTs was added. With the addition of 1wt% reinforcement-a peak value of 4.1 KJ energy absorption was obtained. The homogenous dispersion of CNT-Phenol is thought to be responsible for the considerable enhancement in the reported properties. Copyright © Taylor & Francis Group, LLC.

  2. Diphenylphosphino Styrene-Containing Homopolymers: Influence of Alkylation and Mobile Anions on Physical Properties. (United States)

    Jangu, Chainika; Schultz, Alison R; Wall, Candace E; Esker, Alan R; Long, Timothy E


    Conventional free radical polymerization and post-alkylation of 4-diphenylphosphino styrene (DPPS) generate a new class of high-molecular-weight phosphonium-containing homopolymers with tunable thermal, viscoelastic, and wetting properties. Post-alkylation and subsequent anion exchange provide an effective method for tuning Tg values and thermal stability as a function of alkyl chain length and counteranion selection (X(-) , BF4 (-) , TfO(-) , and Tf2 N(-) ). Rheological characterization facilitates the generation of time-temperature-superposition (TTS) pseudomaster curves and subsequent analysis of frequency sweeps at various temperatures reveals two relaxation modes corresponding to long-range segmental motion and the onset of viscous flow. Contact angle measurements reveal the influence of counteranion selection on wetting properties, revealing increased contact angles for homopolymers containing nucleophilic counteranions. These investigations provide fundamental insight into phosphonium-containing polymers, aiming to guide future research and applications involving electro-active polymeric devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Carbon nanotube buckypaper reinforced acrylonitrile-butadiene-styrene composites for electronic applications. (United States)

    Díez-Pascual, Ana M; Gascón, David


    Novel acrylonitrile-butadiene-styrene (ABS) nanocomposites reinforced with pristine or functionalized single- or multiwalled carbon nanotube buckypaper (BP) sheets were manufactured via hot-compression and vacuum infiltration. Their morphology, thermal, mechanical, and electrical properties were comparatively investigated. Scanning electron microscopy and thermogravimetric analysis showed that the infiltration process leads to better BP impregnation than the hot-press technique. BPs made from functionalized or short nanotubes form compact networks that hamper the penetration of the matrix chains, whereas those composed of pristine tubes possess large pores that facilitate the polymer flow, resulting in composites with low degree of porosity and improved mechanical performance. Enhanced thermal and electrical properties are found for samples incorporating functionalized BPs since dense networks lead to more conductive pathways, and a stronger barrier effect to the diffusion of degradation products, thus better thermal stability. According to dynamic mechanical analysis these composites exhibit the highest glass transition temperatures, suggesting enhanced filler-matrix interactions as corroborated by the Raman spectra. The results presented herein demonstrate that the composite performance can be tailored by controlling the BP architecture and offer useful insights into the structure-property relationships of these materials to be used in electronic applications, particularly for EMI shielding and packaging of integrated circuits.

  4. Electromechanical properties of poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) films. (United States)

    Okuzaki, Hidenori; Suzuki, Hiroki; Ito, Takamichi


    Free-standing films made of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT/PSS) were prepared by casting water dispersion of its colloidal particles. Morphology, water vapor sorption, and electro-active polymer actuating behavior of the resulting films were investigated by means of atomic force microscopy, sorption isotherm, thermal mechanical analysis, and electromechanical analysis. It was found that the PEDOT/PSS film sorbed 60% of moisture at relative water vapor pressure of 0.95. Upon application of 10 V, the film underwent contraction of 2.4% in air at 50% relative humidity (RH) which significantly increased to 4.5% at 90% RH. The principle lay in desorption of water vapor sorbed in the film due to Joule heating, where electric field was capable of controlling the equilibrium of water vapor sorption. The film generated contractile stress as high as 17 MPa under isometric conditions and work capacity attained 174 kJ m(-3), where Young's modulus of the film increased from 1.8 to 2.6 GPa by application of 6 V at 50% RH.

  5. Nickel ion removal using nanoporous poly(styrene-co divinyl benzene) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Bagherian, Abbas; Ghorbani, Mohsen; Mirzababaei, Seyed Nima [Babol University of Technology, Babol (Iran, Islamic Republic of)


    To achieve a suitable porous structure and high mechanical strength that is extremely valuable properties in adsorbent polymeric particles, poly(styrene-co-divinylbenzene) with high amounts of cross-linker and diverse proportions of diluent agent (porogen) were synthesized according to the methodology of the suspension polymerization technique. The structural characteristics of the particles and their adsorption properties for adsorption of Nickel ions were studied. Effect of solvent type and monomeric fraction on particles morphology and porosity was discussed. The solvents including n-heptane (HEP) and acetonitrile and monomer fraction was 50% and 30% of divinylbenzene (DVB). From the results obtained, we decided to apply an adsorbent with high mechanical strength and a porous structure appropriate for absorbing the Ni(II). The copolymer was characterized by Fourier transform infrared (FT-IR) analysis. We used scanning electron microscopy (SEM) and transmission electron microscopy (TEM) tests to study the morphology and particle size of the nanoparticles. According to the results, the copolymers synthesized with n-heptane have more porosity. Also an increase in the percentage of DVB caused finer pores. After synthesis of copolymer the applicability of these polymer beads to separation and concentration of Ni(II) is discussed. In separation of Ni(II) from aqueous solution, the effects of pH, temperature and time are discussed and thermodynamic and kinetic calculations are done and its isotherm are fitted with various equations.

  6. Styrene exposure and biologic monitoring in FRP boat production plants

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, M.; Koizumi, A.; Miyasaka, M.; Watanabe, T.


    A survey on styrene exposure was conducted in five small to medium-sized fiber-reinforced plastic (FRP) boat plants utilizing carbon felt dosimeters as personal and stationary samplers to measure 4h (TWA) exposure during workday afternoons. The heaviest exposure, up to 256 ppm by personal sampling and 174 ppm by stationary sampling, took place during the lamination on a mold to produce a boat shell, and the work inside narrow holds also resulted in exposures of a comparable degree. Styrene levels were much lower in other auxiliary works. The TWA of exposure in an entire boat production was estimated to be 40-50 ppm. Installation of several flexible hoses as an exhaust system was proved to be effective in decreasing the vapor concentration. Gas masks were also useful in reducing the exposure. Urine samples were collected from 96 male workers at the end of 8h work (4h in the morning and 4h in the afternoon) and also from 22 nonexposed male subjects, and analyzed for mandelic acid (MA), phenylglyoxylic acid (PhGA), and hippuric acid (HA). When the results of urinalyses were compared with 4-h styrene TWA as monitored by personal sampling, the best correlation was obtained with MA + PhGA/creatinine (the correlation coefficient, 0.88), followed by MA (0.84). For these two cases, regression lines and 95% confidence limits for the group means and for the individual values were calculated. The urinary level of MA, PhGA, and HA in the 22 nonexposed male subjects were also tabulated.

  7. New improved polymer electrolyte membrane for PEM fuel cell. Final Report, 1. Documentation synthesis and test of proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Lund, Peter B.; Dimitrov, I. (IRD A/S, Svendborg (Denmark)); Jankova, K.; Hvilsted, S. (Technical Univ. of Denmark. Chemical Engineering, Kgs. Lyngby (Denmark)); Juul Larsen, M.; Skou, E. (Univ. of Southern Denmark. Institute of Chemical Engineering, Biotechnology and Environmental Technology, Odense (Denmark))


    A novel concept for preparation of sulfonate containing fluorinated block co-polystyrenes have been developed based on initial ATRP of fluorinated styrene monomers. The strategy depends on well defined macroinitiatiors that after conversion to block copolymers can be post functionalized in two steps with propyl sulfonate groups in different ratios. Thermal investigations have demonstrated that addition of a PFS block to the sulfonate containing block improves the materials' thermal stability. (Author)


    The report gives results of emissions measurements carried out at a representative facility (Eljer Plumbingware in Wilson, NC) that manufactures polyester-resin-reinforced shower stalls and bathtubs by spraying styrene-based resins onto molds in vented, open, spray booths. Styren...


    This report is an addendum to a 1996 report, Assessment of Styrene Emission Controls for FRP/C and Boat Building Industries. It presents additional evaluation of the biological treatment of styrene emissions, Dow Chemical Company's Sorbathene solvent vapor recovery system, Occupa...

  10. 21 CFR 177.2710 - Styrene-divinylbenzene resins, cross-linked. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-divinylbenzene resins, cross-linked. 177.2710 Section 177.2710 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... resins, cross-linked. Styrene-divinylbenzene cross-linked copolymer resins may be safely used as articles...

  11. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene... (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, condensated... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

  12. 21 CFR 173.70 - Chloromethylated aminated styrene-divinylbenzene resin. (United States)


    ... resin. 173.70 Section 173.70 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... Chloromethylated aminated styrene-divinylbenzene resin. Chloromethylated aminated styrene-divinylbenzene copolymer... resin dispersion. (c) The additive is used as a decolorizing and clarification agent for treatment of...

  13. Utilizing the phenol byproducts of coke production: 3. Phenols as coinhibitors of thermopolymerization during styrene production

    Energy Technology Data Exchange (ETDEWEB)

    I.I. Batura; A.F. Gogotov; V.I. Cherepanov; O.I. Baranov; A.A. Levchuk; M.V. Parilova [Irkutsk State Technical University, Irkutsk (Russian Federation)


    A new oligomerization procedure for phenol byproducts from coke production is experimentally studied. This method, oxidative combination, is intended to produce an effective coinhibitor of styrene thermopolymerization. When combined with a Mannich base, the new oligomer exhibits excellent inhibiting properties in the heat treatment of styrene and matches the effectiveness of imported inhibitors based on nitroxyl radicals. 15 refs., 1 tab.

  14. Exploiting Framework Flexibility of a Metal-Organic Framework for Selective Adsorption of Styrene over Ethylbenzene

    NARCIS (Netherlands)

    Mukherjee, S.; Joarder, B.; Desai, A.V.; Manna, B.; Krishna, R.; Ghosh, S.K.


    The separation of styrene and ethylbenzene mixtures is industrially important and is currently performed in highly energy-intensive vacuum distillation columns. The primary objective of our investigation is to offer an energy-efficient alternative for selective adsorption of styrene by a flexible

  15. Research of operational properties of compound based on high viscosity styrene-butadiene rubber SSBR-2560 TDAE HV

    Directory of Open Access Journals (Sweden)

    M. I. Falyakhov


    Full Text Available The article consider the influence of replacement of SSBR-2560 TDAE batch production on high viscosity SSBR-2560-TDAE HV in the tread recipe on the tire performance properties. Obtained samples were highly viscosity styrene butadiene rubber did not differ in the microstructure of the SSBR-2560 TDAE batch production. Increasing the molecular weight possible to increase the Mooney viscosity of the rubber, however, is known to one of adverse factors is the deterioration of processability of rubber compounds based on polymers. In this connection, investigated the behavior in the step mixing compound based on high viscosity SSBR rubber. We chose recipes tread of the tire with a high content of organic silicon filler. It is established that the equivalent replacement of the polymer in the tread recipe does not lead to significant changes in the basic parameters of rubber mixing. We observed a slight increase in the energy consumption for the preparation of the rubber compounds, as well as the discharge temperature at each stage. It was shown to improve the distribution of the filler in the polymer matrix for the compound based on SSBR-2560 TDAE HV. The results showed that compound based on high viscosity SSBR improves rolling resistance and traction characteristics, while maintaining abrasion in comparison with the SSBR-2560-M27 batch production. Recommended use this brand in the production of rubber car tires.

  16. Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups. (United States)

    Zhang, Yu-Chen; Jiang, Fei; Wang, Shu-Liang; Shi, Feng; Tu, Shu-Jiang


    The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.

  17. Human exposure to styrene. IV. Industrial hygiene investigations and biological monitoring in the polyester industry

    Energy Technology Data Exchange (ETDEWEB)

    Guillemin, M.P.; Bauer, D.; Martin, B.; Marazzi, A.


    An industrial hygiene study of 10 glassfiber reinforced polyester plants (including 90 workers) was undertaken to investigate the styrene exposure in this industry and to estimate biological limit values (BLV's) for the urinary metabolites of styrene: mandelic (MA) and phenylglyoxylic acids (PGA). Time weighted average (TWA) styrene exposures were found ranging from 2 to 200 ppm. The urinary elimination of metabolites correlated well with exposure and the BLV's corresponding to an 8-h exposure at 100 ppm were consistent with earlier laboratory findings (end-of-shift sample: MA 1640, PGA 510, MA + PGA 2150; next-morning sample: MA 330, PGA 330, MA + PGA 660 mg/g creat.). Total metabolites (MA + PGA) in the next-morning sample or mandelic acid in the end-of-shift sample are recommended for routine monitoring of exposure to styrene. The study revealed the need for further research on how to reduce styrene exposure in this industry.

  18. No acute behavioral effects of exposure to styrene: a safe level of exposure

    Energy Technology Data Exchange (ETDEWEB)

    Edling, C.; Ekberg, K.


    To determine whether exposure to low levels of styrene (below 110 mg/m3) causes acute behavioral effects and symptoms that may be related to concentrations of styrene in air or urinary mandelic acid or both, 12 men occupationally exposed to styrene were studied and compared with a reference group of 10 unexposed men. Simple reaction time was measured before and after work and information about symptoms was obtained by questionnaire. Active and passive sampling of airborne styrene was carried out and urinary mandelic acid concentrations were measured. Although the size of the study groups is small, the results indicate that exposure to styrene below 110 mg/m3 does not cause any acute adverse effects on the central nervous system.

  19. 40 CFR 63.500 - Back-end process provisions-carbon disulfide limitations for styrene butadiene rubber by emulsion... (United States)


    ... disulfide limitations for styrene butadiene rubber by emulsion processes. 63.500 Section 63.500 Protection... limitations for styrene butadiene rubber by emulsion processes. (a) Owners or operators of sources subject to this subpart producing styrene butadiene rubber using an emulsion process shall operate the process...

  20. Fluorescent 'two-faced' polymer wafers with embedded pyrene-functionalised gelator nanofibres. (United States)

    Moffat, Jamie R; Smith, David K


    Pyrene-functionalised gelators self-assemble into nano-fibrillar organogels in DMSO/styrene/divinylbenzene mixtures, which when polymerised yield polymer wafers with two distinct faces, only one of which is fluorescent and has embedded gelator nanofibres. This journal is © The Royal Society of Chemistry 2011

  1. Electron-enhanced hole injection in blue polyfluorene-based polymer light-emitting diodes

    NARCIS (Netherlands)

    Woudenbergh, T. van; Wildeman, J.; Blom, P.W.M.; Bastiaansen, J.J.A.M.; Langeveld-Voss, B.M.W.


    It has recently been reported that, after electrical conditioning, an ohmic hole contact is formed in poly(9,9-dioctylfluorene) (PFO)-based polymer light-emitting diodes (PLED), despite the large hole-injection barrier obtained with a poly(styrene sulfonic acid)-doped


    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  3. Heart block (United States)

    ... page: // Heart block To use the sharing features on this page, ... Date 4/16/2017 Updated by: Michael A. Chen, MD, PhD, Associate Professor of Medicine, Division of ...

  4. Evaluation of acrylate-based block copolymers prepared by atom transfer radical polymerization as matrices for paclitaxel delivery from coronary stents. (United States)

    Richard, Robert E; Schwarz, Marlene; Ranade, Shrirang; Chan, A Ken; Matyjaszewski, Krzysztof; Sumerlin, Brent


    Acrylate-based block copolymers, synthesized by atom transfer radical polymerization (ATRP) processes, were evaluated as drug delivery matrices for the controlled release of paclitaxel from coronary stents. The polymers were multiblock copolymers consisting of poly(butyl acrylate) or poly(lauryl acrylate) soft blocks and hard blocks composed of poly(methyl methacrylate), poly(isobornyl acrylate), or poly(styrene) homo- or copolymers. Depending on the ratio of hard to soft blocks in the copolymers, coating formulations were produced that possessed variable elastomeric properties, resulting in stent coatings that maintained their integrity when assessed by scanning electron microscopy (SEM) imaging of overexpanded stents. In vitro paclitaxel release kinetics from coronary stents coated with these copolymers typically showed an early burst followed by sustained release behavior, which permitted the elution of the majority of the paclitaxel over a 10-day time period. It was determined that neither the nature of the polyacrylate (n-butyl or lauryl) nor that of the hard block appeared to affect the release kinetics of paclitaxel at a loading of 25% drug by weight, whereas some effects were observed at lower drug loading levels. Differential scanning calorimetry (DSC) analysis indicated that the paclitaxel was at least partially miscible with the poly(n-butyl acrylate) phase of those block copolymers. The copolymers were also evaluated for sterilization stability by exposing both the copolymer alone and copolymer/paclitaxel coated stents to e-beam radiation at doses of 1-3 times the nominal dose used for medical device sterilization (25 kGy). It was found that the copolymers containing blocks bearing quaternary carbons within the polymer backbone were less stable to the radiation and showed a decrease in molecular weight as determined by gel-permeation chromatography. Conversely, those without quaternary carbons showed no significant change in molecular weight when

  5. Thin Films of Block Copolymers/Homopolymer: Effect of Non-Adsorbing Block Length on the Interfacial Properties (United States)

    Costa, Ana Claudia; Composto, Russell J.; Vlcek, Petr; Geoghehan, Mark; Creton, Costantino


    We have addressed the effect of non-adsorbing block length of block copolymers on their interfacial properties. To this goal, a low volume fraction (5 vol.styrene-b-methylmethacrylate) (dPS-b-MMA) having a nearly constant adsorbing block length (NMMA 40) was added to a PS matrix, which represents a nearly neutral environment for the dPS block. Films with varying non-adsorbing block lengths (NdPS 90-940) were spin coated on silicon oxide surfaces. Neutron reflectivity and forward recoil spectrometry were used to measure the dPS-b-MMA interfacial excess (z*) and width (w). The results show that z* and w increases with NdPS. These results are interpreted using a self-consistent mean field model. Probe tack tests indicate that adhesion improves with NdPS and suggests that the entanglements across the matrix/adsorbed layer interface are partially responsible for enhanced thin film adhesion.

  6. Green polymer chemistry: biocatalysis and biomaterials (United States)

    This overview briefly surveys the practice of green chemistry in polymer science. Eight related themes can be discerned from the current research activities: 1) biocatalysis, 2) bio-based building blocks and agricultural products, 3) degradable polymers, 4) recycling of polymer products and catalys...

  7. Solution Behavior of Responsive Cationic Polymers


    Karjalainen, Erno


    This thesis combines anion responsive polymeric ionic liquids (PILs) with thermoresponsive polymers. The polymers have been synthesized with controlled radical polymerization methods. A water-insoluble PIL was used as a macro-chain transfer agent in synthesis of block copolymers with poly(N-isopropyl acrylamide) (PNIPAm). PNIPAm chains of various lengths were grown to the same PIL-block. These polymers show a lower cirical solution temperature (LCST) type behavior, typical to PNIPAm. The...

  8. Positron annihilation lifetime study of interfaces in ternary polymer blends (United States)

    Meghala, D.; Ramya, P.; Pasang, T.; Raj, J. M.; Ranganathaiah, C.; Williams, J. F.


    A new method based on positron lifetime spectroscopy is developed to characterize individual interfaces in ternary polymer blends and hence determine the composition dependent miscibility level. The method owes its origin to the Kirkwood-Risemann-Zimm (KRZ) model for the evaluation of the hydrodynamic interaction parameters (αij) which was used successfully for a binary blend with a single interface. The model was revised for the present work for ternary polymer blends to account for three interfaces. The efficacy of this method is shown for two ternary blends namely poly(styrene-co-acrylonitrile)/poly (ethylene-co-vinylacetate)/poly(vinyl chloride) (SAN/EVA/PVC) and polycaprolactone /poly(styrene-co-acrylonitrile)/poly(vinyl chloride) (PCL/SAN/PVC) at different compositions. An effective hydrodynamic interaction parameter, αeff, was introduced to predict the overall miscibility of ternary blends.

  9. The tonotopicity of styrene-induced hearing loss depends on the associated noise spectrum. (United States)

    Venet, Thomas; Campo, Pierre; Thomas, Aurélie; Cour, Chantal; Rieger, Benoît; Cosnier, Frédéric


    The neuropharmacological and cochleotoxic effects of styrene can exacerbate the impact of noise on the peripheral auditory receptor. The mechanisms through which co-exposure to noise and styrene impairs hearing are complex as the slowly developing cochleotoxic process can be masked in the short-term by the rapid pharmacological effect on the central nervous system. The current investigation was therefore designed to delineate the auditory frequency range sensitive to noise, to styrene, and to noise and styrene combined. In case of different frequency ranges targeted by noise and styrene, it would be possible to point out the main factor responsible for cases of deafness by looking at the location of the audiometric deficits. Male Brown-Norway rats were exposed to 600-ppm styrene, to an octave band noise centered at 8 kHz, or to both noise and styrene. The noise exposure was of two different types: impulse noise with a LEX,8h (equivalent continuous noise level averaged over 8 h) of 80 dB and continuous noise with a LEX,8 h of 85 dB SPL. Hearing was tested using a non-invasive technique based on distortion product otoacoustic emissions. Hearing data were completed with histological analysis of cochleae. The results showed that exposure to styrene alone caused outer hair cell losses in the apical cochlear region, which discriminates low frequencies. In contrast, noise-induced hearing loss was located at half an octave above the central frequency of the spectrum, around 10-12 kHz. Damage due to impulse noise was significantly exacerbated by styrene, and the noise spectrum defined the location of the cochlear trauma. Combined exposure caused greater cell losses than the sum of losses measured with the impulse noise and styrene alone. The fact that the tonotopicity of the styrene-induced damage depends on the associated noise spectrum complicates the diagnosis of styrene-related hearing loss with a tone-frequency audiometric approach. In conclusion, there is not really a

  10. Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile-butadiene-styrene model samples and historical objects. (United States)

    Saviello, Daniela; Pouyet, Emeline; Toniolo, Lucia; Cotte, Marine; Nevin, Austin


    Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile-butadiene-styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3×3 μm(2)) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer. (United States)

    Brebu, Mihai; Bhaskar, Thallada; Murai, Kazuya; Muto, Akinori; Sakata, Yusaku; Uddin, Md Azhar


    Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.

  12. Mechanical and Electrical Properties of Styrene-Isoprene-Styrene Copolymer Doped with Expanded Graphite Nanoplatelets

    Directory of Open Access Journals (Sweden)

    Zdenko Špitalský


    Full Text Available The molecular dynamics of a triblock copolymer and of expanded graphite nanoplatelets were investigated. Composites were prepared using the solution technique. The effects of filler addition and of filler-matrix interactions were investigated using dielectric relaxation spectroscopy (DRS and dynamic mechanical analysis (DMA. Only one relaxation was observed by DRS, which was associated with the relaxation of the main polymer chain. Both DRS and DMA demonstrated that the addition of the filler does not cause a significant change in either the temperature of the relaxation or its activation energy, which suggests the presence of weak interactions between the filler and matrix. The storage modulus of the composites increased with increasing filler content. The composite containing 8% filler exhibited a storage modulus increase of approximately 394% in the rubber area. Using the DC electrical conductivity measurements, the electrical percolation threshold was determined to be approximately 5%. The dielectric permittivity and conductivity in the microwave region were determined, confirming that percolating behavior and the critical threshold concentration.

  13. High elastic modulus polymer electrolytes (United States)

    Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel


    A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics.

  14. Low level occupational exposure to styrene: its effects on DNA damage and DNA repair. (United States)

    Wongvijitsuk, Sirilak; Navasumrit, Panida; Vattanasit, Udomratana; Parnlob, Varabhorn; Ruchirawat, Mathuros


    The present study aimed to evaluate the effects of styrene exposure at levels below the recommended standards of the Threshold Limit Value (TLV-TWA(8)) of 20 ppm (ACGIH, 2004) in reinforced-fiberglass plastics workers. Study subjects comprised 50 exposed workers and 40 control subjects. The exposed workers were stratified by styrene exposure levels, i.e. group I (20 ppm, >84.40 mg/m(3)). The mean styrene exposure levels of exposed workers were significantly higher than those of the control workers. Biomarkers of exposure to styrene, including blood styrene and the urinary metabolites, mandelic acid (MA) and phenylglyoxylic acid (PGA), were significantly increased with increasing levels of styrene exposure, but were not detected in the control group. DNA damage, such as DNA strand breaks, 8-hydroxydeoxyguanosine (8-OHdG), and DNA repair capacity, were used as biomarkers of early biological effects. DNA strand breaks and 8-OHdG/10(5)dG levels in peripheral leukocytes of exposed groups were significantly higher compared to the control group (Prisk from occupational styrene exposure, even at levels below the recommended TLV-TWA(8) of 20 ppm. Copyright © 2010 Elsevier GmbH. All rights reserved.

  15. A multicenter study on the audiometric findings of styrene-exposed workers. (United States)

    Morata, Thais C; Sliwinska-Kowalska, Mariola; Johnson, Ann-Christin; Starck, Jukka; Pawlas, Krystyna; Zamyslowska-Szmytke, Ewa; Nylen, Per; Toppila, Esko; Krieg, Edward; Pawlas, Natalia; Prasher, Deepak


    The objective of this study was to evaluate hearing loss among workers exposed to styrene, alone or with noise. This cross-sectional study was conducted as part of NoiseChem, a European Commission 5th Framework Programme research project, by occupational health institutes in Finland, Sweden, and Poland. Participants' ages ranged from 18-72 years (n = 1620 workers). Participants exposed to styrene, alone or with noise, were from reinforced fiberglass products manufacturing plants (n = 862). Comparison groups were comprised of workers noise-exposed (n = 400) or controls (n = 358). Current styrene exposures ranged from 0 to 309 mg/m(3), while mean current noise levels ranged from 70-84 dB(A). Hearing thresholds of styrene-exposed participants were compared with Annexes A and B from ANSI S3.44, 1996. The audiometric thresholds of styrene exposed workers were significantly poorer than those in published standards. Age, gender, and styrene exposure met the significance level criterion in the multiple logistic regression for the binary outcome 'hearing loss' (P = 0.0000). Exposure to noise (risk factor for hearing loss, and styrene-exposed workers should be included in hearing loss prevention programs.

  16. Leaching of styrene and other aromatic compounds in drinking water from PS bottles. (United States)

    Ahmad, Maqbool; Bajahlan, Ahmad S


    Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene (PS) bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as "purge and trap" and analysed by gas chromatograph-mass spectrometer (GC/MS). Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 microg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 microg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.

  17. Trends in occupational exposure to styrene in the European glass fibre-reinforced plastics industry. (United States)

    Van Rooij, J G M; Kasper, A; Triebig, G; Werner, P; Jongeneelen, F J; Kromhout, H


    This study presents temporal trends of styrene exposure for workers in the European glass fibre-reinforced plastics (GRP) industry during the period 1966-2002. Data of personal styrene exposure measurements were retrieved from reports, databases and peer-reviewed papers. Only sources with descriptive statistics of personal measurements were accepted. The styrene exposure data cover personal air samples and biological monitoring data, that is, urinary styrene metabolites (mandelic acid and/or phenylglyoxylic acid) and styrene in blood. Means of series of measurements were categorized by year, country, production process, job and sampling strategy. Linear mixed models were used to identify temporal trends and factors affecting exposure levels. Personal exposure measurements were available from 60 reports providing data on 24145 1-8-h time-weighted average shift personal air samples. Available data of biological exposure indicators included measurements of mandelic acid in post-shift urine (6361 urine samples being analysed). Trend analyses of the available styrene exposure data showed that the average styrene concentration in the breathing zone of open-mould workers in the European GRP industry has decreased on average by 5.3% per year during the period 1966-1990 and by only 0.4% annually in the period after 1990. The highest exposures were measured in Southern Europe and the lowest exposures in Northern Europe with Central Europe in between. Biological indicators of styrene (mandelic acid in post-shift urine) showed a somewhat steeper decline (8.9%), most likely because urine samples were collected in companies that showed a stronger decrease of styrene exposure in air than GRP companies where no biological measurements were carried out.

  18. 77 FR 65831 - Polymers; exemptions from the requirement of a tolerance. (United States)


    ... AGENCY 40 CFR Part 180 -( -Nonylphenyl)poly(oxypropylene) Block Polymer With Poly(oxyethylene); Tolerance...) block polymer with poly(oxyethylene); when used as an inert ingredient in a pesticide chemical... establish a maximum permissible level for residues of - ( -Nonylphenyl)poly(oxypropylene) block polymer with...

  19. Perfluorinated polymer grafting: influence of preirradiation conditions

    Energy Technology Data Exchange (ETDEWEB)

    Moura, E.; Somessari, E.S.R.; Silveira, C.G.; Paes, H.A.; Sousa, C.A.; Fernandes, W.; Manzoli, J.E; Geraldo, A.B., E-mail: ageraldo@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Cardozo, P. [Universidade Sao Judas Tadeu, Sao Paulo, SP (Brazil)


    The technological interest of perfluorinated polymers is related to its specific properties like low chemical reactivity and high mechanical and temperature resistance. The development of polymeric membranes for PEM fuel cell dispositives requires beyond these characteristics, a long-life time performance and low cost compared to Nafion membranes. By these material have high crystallinity, the radiation grafting indeed occurs but this process generate a low mechanical resistance aggregate. In this way, it is necessary to render the polymer with a low crystallinity or even amorphous. Generally, irradiation under polymer melt temperatures makes the crystallinity breaking and polymer crosslinking. The main objective of this work was promoting the crosslinking process into perfluorinated polymers by pre-irradiation method and to precede styrene grafting by electron beam irradiation in a second step. The experimental methodology consists in pre-irradiate perfluorinated polymers films like PTFE and PFA under high temperature (> 300 deg C) and vacuum conditions by electron beam irradiation at 5 kGy to 30 kGy doses and 2,85 kGy/s to 22,4 kGy/s dose rates. To obtain temperatures above 300 deg C, it was necessary construct a vacuum chamber with a heating system where temperature process could be follow up in real time. Some molecular alterations in polymeric matrix were analyzed by Mid-ATR-FTIR spectroscopy; macroscopic changes are verified by gravimetry. The styrene grafting onto these samples is realized by electron beam irradiation at doses between 30 and 100 kGy. These results are discussed. (author)

  20. Chain exchange in block copolymer micelles (United States)

    Lu, Jie; Bates, Frank; Lodge, Timothy


    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  1. Reactive processing of recycled polycarbonate/acrylonitrile butadiene styrene. (United States)

    Jung, Woo-Hyuk; Choi, Yeon-Sil; Moon, Jung-Min; Tortorrela, Nathan; Beatty, Charles L; Lee, Jang-Oo


    Cellular phone housings were ground to make original particulates using a knife mill. Foams and adhesives with a lighter density than water were removed from ground mixtures using a sink-float process in water; ground metals, button rubbers, and wires were separated from desired materials by using a sink float process in salt All housing materials, consisting of seven thermoplastics included in cellular phone housings, showed better tensile properties than pure housing materials made of polycarbonate/acrylonitrile butadiene styrene, but they only had about half of the impact strength. In contrast, the low impact strength for all housing materials was improved by adding 25 wt % polyethylene elastomer and/or 2.4 wt % ground epoxy circuit boards for batch mixing. Impact strengths, tensile strengths, and the energy absorption ability of all housing materials were improved by adding 5.4wt% glycidyl methacrylate for twin screw extrusion.

  2. Interacting Blends of Novel Unsaturated Polyester Amide Resin with Styrene

    Directory of Open Access Journals (Sweden)

    Hasmukh S. Patel


    Full Text Available Novel unsaturated poly (ester-amide resins (UPEAs were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol–A (DGEBA and unsaturated aliphatic bisamic acids using a base catalyst. These UPEAs were then blended with a vinyl monomer namely, Styrene (STY. to produce a homogeneous resin syrup. The curing of these UPEAs-STY. resin blends was carried out by using benzoyl peroxide (BPO as a catalyst and was monitored by using a differential scanning calorimeter (DSC. The glass fibre reinforced composites (i.e. laminates of these UPEA-STY. resin blends were fabricated using the DSC data. The chemical, mechanical and electrical properties of the glass fibre composites have also been evaluated. The unreinforced cured samples of the UPEA-STY. resin blends were also analyzed by thermogravimetry (TGA.

  3. Impaired colour discrimination among workers exposed to styrene: relevance of a urinary metabolite.


    Eguchi, T.; Kishi, R.; Harabuchi, I; Yuasa, J; Arata, Y; Katakura, Y; Miyake, H.


    OBJECTIVES--To survey the loss of colour vision among Japanese workers who have been exposed to styrene concentrations currently considered low (about 20 ppm). Also to assess the effects of styrene by examination of the nature of the relation between disorder of colour vision and age, alcohol consumption, and other variables. METHODS--Colour discrimination was examined in 64 male workers exposed to styrene (mean age; 38.0, mean exposed years; 7.0) and in 69 controls (mean age; 38.0). A standa...

  4. LF-NMR study of effect the octadecylamine addition in the copolymerization process between acrylic acid and styrene monomers; Estudo por RMN de baixo campo do efeito da adicao de octadecilamina na copolimerizacao dos monomeros de acido acrilico e estireno

    Energy Technology Data Exchange (ETDEWEB)

    Pedroza, Oscar J.O.; Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano]. E-mail:,


    The copolymer content at least two monomer units that are the repetitive unities in the polymeric chains. The use of Low Field Nuclear Magnetic Resonance (LF-NMR), MARAN ultra 23, was applied to measure the proton spin-lattice relaxation time values. The process of copolymerization between the acrylic acid (A) and the styrene (S) monomers was studied with the addition of the octadecylamine (D) in the acrylic acid monomer. These materials were submitted at reflux by 24 hours. After this process the polymerization was carried out at room temperature. The values of the relaxation parameter are showed in Table 1. The co polymerizations between acrylic acid and styrene monomers were influenced by the octadecylamine addition. The results showed that an increase in the amine concentration promotes flexibility in the final material. This can be explained in terms of chains size after amine addition, which promotes an increasing in the free space among the polymer chains. (author)

  5. Biodegradable Polymers


    Isabelle Vroman; Lan Tighzert


    Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources) or from biological resources (renewable resources). In general natural polymers offer fewer advantages than synthetic polymers. ...

  6. Viscoelastic behaviour of rubberwood-polymer composites (United States)

    Chan, K. Y.; Yap, M. G. S.; Chia, L. H. L.; Teoh, S. H.

    The dynamic storage modulus E' of rubberwood ( Hevea braziliensis) increased after the in situ polymerization of methylmethacrylate in the wood cellular structure. A significant linear relationship existed between the percentage increase in E' and polymer loading. A thermal scan of tan δ values between -120° and 200°C revealed that the damping pattern of rubberwood was affected to different extents by three different polymeric systems. Poly(styrene- co-acrylonitrile) caused the greatest change in the damping pattern, followed by polymethylmethacrylate-dioxane, and polymethylmethacrylate. This observed trend was attributed to the relative extent of monomer penetration and interaction with the wood cell-wall components.

  7. Smooth Nanowire/Polymer Composite Transparent Electrodes

    KAUST Repository

    Gaynor, Whitney


    Smooth composite transparent electrodes are fabricated via lamination of silver nanowires into the polymer poly-(4,3-ethylene dioxythiophene): poly(styrene-sulfonate) (PEDOT:PSS). The surface roughness is dramatically reduced compared to bare nanowires. High-efficiency P3HT:PCBM organic photovoltaic cells can be fabricated using these composites, reproducing the performance of cells on indium tin oxide (ITO) on glass and improving the performance of cells on ITO on plastic. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Smooth nanowire/polymer composite transparent electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Gaynor, Whitney; McGehee, Michael D. [Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305 (United States); Burkhard, George F. [Department of Applied Physics, Stanford University, Stanford, CA 94305 (United States); Peumans, Peter [Department of Electrical Engineering, Stanford University, Stanford, CA 94305 (United States)


    Smooth composite transparent electrodes are fabricated via lamination of silver nanowires into the polymer poly-(4,3-ethylene dioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS). The surface roughness is dramatically reduced compared to bare nanowires. High-efficiency P3HT:PCBM organic photovoltaic cells can be fabricated using these composites, reproducing the performance of cells on indium tin oxide (ITO) on glass and improving the performance of cells on ITO on plastic. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Modification of asphaltic concrete with a mineral polymeric additive based on butadiene-styrene rubber and chemically precipitated calcium carbonate

    Directory of Open Access Journals (Sweden)

    S. I. Niftaliev


    Full Text Available Modification of asphaltic concrete with a mineral polymeric additive based on butadiene – styrene rubber and chemically precipitated calcium carbonate. This paper presents the results of the study of physical – mechanical and service properties of the asphaltic concrete modified with the mineral polymeric composition. Calcium carbonate is used both as a filler and a coagulant. The chalk was preliminarily ground and hydrophobizated by stearic acid. These operations contribute to even distribution of the filler and interfere with lump coagulation. As a result of the experiments, it was found that the best results were obtained by combining the operations of dispersion and hydrophobization. The optimal amount of stearic acid providing the finest grinding in a ball mill is a content from 3 to 5% by weight. The optimal grinding time of the filler was found (4–6 hours. With increasing dispersion time the particles form agglomerates. Filling the butadiene styrene latex with the hydrophobic fine-grained calcium carbonate was carried out in the laboratory mixer. As a result of the experimental works, it was found that the best distribution of the filler takes place with ratio of rubber: chalk – 100:400. The resulting modifier was subjected to the thermal analysis on the derivatograph to determine its application temperature interval. A marked reduction in weight of the mineral polymeric modifier begins at 350 °C. Thus, high temperature of the modifier destruction allows to use it at the temperature of the technological process of asphaltic concrete preparation (up to 170 °C. It was found that an increase in the amount of the carbonate filler in the rubber SKS 30АRК significantly increases its thermal resistance and connection of the polymer with the chalk in the composition.

  10. Interfacial structure and dynamics of polymeric materials. I. Perfluoropolyether lubricant on solid substrate. II. Two-dimensional self-assembly of linear-nanoparticle block copolymers (United States)

    Kim, Yoojin

    We have studied two systems of thin polymer films on solid surfaces. The first study has examined the effects of surface confinement in the backbone dynamics of a hard disk drive lubricant, Zdol, on silica and amorphous carbon surfaces. The second study has allowed us to investigate the effect of architecture on the block copolymer self-assembly at the air-water interface and on a solid surface in a straightforward fashion. Carbon-13 and fluorine-19 solid-state NMR techniques have been used to compare the various backbone dynamics of Zdol in the bulk and in ultra-thin films. On a silica surface, the conformational transition of one segment is found to slow down indicating that the interaction of Zdol with the surface hinders such motion. However, the amplitude of the C-F bond libration is slightly increased on the surface due to the elimination of the cohesive interaction with the neighboring molecules. The longer-range motions involving more than one segment in a cooperative fashion are detected by the 19F spin-spin relaxation time (T2) that decreases by two orders of magnitude in thin films. The 19F line width increase and the downfield shift suggest that backbone interacts with the active binding sites of the amorphous carbon surface via electron donation from the ether oxygen lone pairs. We have synthesized a series of poly(ethylene glycol)-b-(styrene- r-benzocyclobutene) block copolymers with different architectures. The linear block copolymer precursor and the linear-nanoparticle block copolymer resulting from selective intramolecular crosslinking of the benzocyclobutene units have exactly the same molecular weight and chemical composition, but different architectures. At the air-water interface, the block copolymers self-assemble into remarkably different surface aggregates. While the linear block copolymer forms disk-like surface assemblies, the linear-nanoparticle block copolymer exhibits long (>10 mum) worm-like aggregates whose length increases as a

  11. In-situ Polymerization of Styrene to Produce Polystyrene / Montmorillonite Nanocomposites

    National Research Council Canada - National Science Library

    Lahouari Mrah; Rachid Meghabar; Mohammed Belbachir


    .... CTAB-intercalated Mmt particles were easily dispersed and swollen in styrene monomer, PS/Mmt-CTAB nanocomposites were synthesized via in-situ polymerization, in-situ polymerization, this method...

  12. Exposure to styrene in fiberglass-reinforced plastic manufacture: still a problem. (United States)

    Papaleo, Bruno; Caporossi, Lidia; Bernardini, Francesca; Cristadoro, Luisa; Bastianini, Lucia; De Rosa, Mariangela; Capanna, Silvia; Marcellini, Laura; Loi, Francesco; Battista, Giuseppe


    The aim of the work is to define occupational exposure to styrene in fiberglass manufacture; the phase of stretching styrene resins needs some manual handling and leads workers to be exposed to styrene. We surveyed 20 workers in two companies manufacturing fiberglass, checking environmental levels and urinary concentrations of mandelic acid (MA), and phenylglioxylic acid (PGA). Workers completed a questionnaire collecting their medical history. Environmental monitoring showed some styrene concentrations higher than the threshold limit value-time-weighted average. Biological monitoring confirmed these findings and four workers had levels of urinary PGA and MA concentrations higher than the Biological Exposure Indices of the American Conference of Governmental Industrial Hygienists. This picture confirms that, even though the risk is known and the manufacturing cycle is well-defined, workers nevertheless risk exposure. More research is needed to optimize the work processes and the protection systems to lower this risk.

  13. Formation of styrene dependent on fermentation management during wheat beer production. (United States)

    Schwarz, Katrin J; Stübner, René; Methner, Frank-Jürgen


    Styrene is formed by the thermal decarboxylation of cinnamic acid during wort boiling or by enzymatic decarboxylation during fermentation. The enzymatic reactions proceed in parallel to the decarboxylation of ferulic- and p-cumaric acid to 4-vinylguaiacol and 4-vinylphenol by the same decarboxylase enzyme. However, the formation of styrene occurs much faster and all available cinnamic acid in wort was converted completely within a few hours. Moreover, the comparison of various manufacturing parameters shows that a higher fermentation temperature of 25 °C compared to 16 °C and an open fermentation management lead to a rapid decrease of styrene. This allows minimising the content of styrene in beer while maintaining the typical wheat beer flavours. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Crack initiation and propagation on the polymeric material ABS (Acrylonitrile Butadiene Styrene), under ultrasonic fatigue testing

    National Research Council Canada - National Science Library

    G M Domínguez Almaraz; E Correa Gómez; JC Verduzco Juárez; JL Avila Ambriz


    ... (Acrylonitrile Butadiene Styrene), under ultrasonic fatigue testing. Three controlled actions were implemented in order to carry out fatigue tests at very high frequency on this material of low thermal conductivity, they are: a...

  15. EPR investigation on radiation-induced graft copolymerization of styrene onto polyethylene: Energy transfer effects

    Energy Technology Data Exchange (ETDEWEB)

    Salih, M.A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Buttafava, A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Ravasio, U. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Dipartimento di Ingegneria Nucleare, Politecnico di Milan (Italy); Mariani, M. [Dipartimento di Ingegneria Nucleare, Politecnico di Milan (Italy); Faucitano, A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy)]. E-mail:


    In this paper, energy transfer phenomena concerning the in-source graft copolymerization of styrene onto LDPE were investigated through the EPR analysis of the radical intermediates. The model solution experiments have shown a substantial deviation of the experimental G (radicals) values with respect to the additivity law, which reflect the negative effect of the styrene monomer concentration on the initiation rate of the graft copolymerization. The EPR measurements performed on polyethylene-co-styrene graft copolymers of various composition following low-temperature vacuum gamma irradiation have confirmed the decrease of the total radical yields with increasing the styrene concentration. The effect was partly attributed to the heterogeneity of the graft copolymer matrix and to the lack of molecular mobility in the solid state at low temperature, which prevents the attainment of the favourable geometrical configurations in intermolecular energy and charge transfer events.

  16. Block copolymer investigations (United States)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  17. Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants. (United States)

    Genualdi, Susan; Nyman, Patricia; Begley, Timothy


    Due to the 2011 labelling of styrene monomer as "reasonably anticipated to be a human carcinogen" by the National Institutes of Health's National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg(-1) for the styrene monomer, 130-2900 mg kg(-1) for the sum of three styrene dimers, and 220-16,000 mg kg(-1) for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g(-1); dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g(-1) and trimer concentrations were all below the LOQ (2 ng g(-1)). Diffusion coefficients (Dp) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10(2) to 2 × 10(6)) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.

  18. Poly(styrene-co-divinylbenzene-co-2-ethylhexyl)acrilate membranes with interconnected macroporous structure


    Sevšek, Urška; Stropnik, Črtomir; Krajnc, Peter; Pulko, Irena; Seifried, Silvo


    A combination of doctor blading and emulsion templating was used to prepare macroporous poly(styrene-co-divinylbenzene-co-2-ethylhexylacrylate) and poly(styrene-co-divinylbenzene) membranes with an interconnected porous structure. Water in oil high internal phase emulsions including monomers in the oil phase were cast onto a glass plate and polymerised at elevated temperature. After purification porous polyHIPE membranes were obtained. The volume ratio of aqueous phase (75 % or 85 %) and the ...

  19. Impact behaviour of acrylonitrile-butadiene-styrene after temperature and humidity load


    Hylova Lenka; Manas Miroslav


    This study deals with acrylonitrile-butadiene-styrene (ABS) which was subjected the drop-weight test before and after temperature and humidity load. ABS is an engineering plastic and also an important engineering terpolymer, which has butadiene part uniformly distributed through the acrylonitrile-styrene matrix and is commonly used in production of automotive interior components. The injection moulded ABS samples were subjected the penetration test at fall height 100 J before and after temper...

  20. Polymer Vesicles as Robust Scaffolds for the Directed Assembly of Highly Crystalline Nanocrystals †

    KAUST Repository

    Wang, Mingfeng


    We report the incorporation of various inorganic nanoparticles (NPs) (PbS, LaOF, LaF3, and TiO2, each capped by oleic acid, and CdSe/ZnS core/shell QDs capped by trioctylphosphine oxide) into vesicles (d = 70-150 nm) formed by a sample of poly(styrene-b-acrylic acid) (PS4o4-b-PAA 62, where the subscripts refer to the degree of polymerization) in mixtures of tetrahydrofuran (THF), dioxane, and water. The block copolymer formed mixtures of crew-cut micelles and vesicles with some enhancement of the vesicle population when the NPs were present. The vesicle fraction could be isolated by selective sedimentation via centrifugation, followed by redispersion in water. The NPs appeared to be incorporated into the PAA layers on the internal and external walls of the vesicles (strongly favoring the former). NPs on the exterior surface of the vesicles could be removed completely by treating the samples with a solution of ethylenediaminetetraacetate (EDTA) in water. The triangular nanoplatelets of LaF3 behaved differently. Stacks of these platelets were incorporated into solid colloidal entities, similar in size to the empty vesicles that accompanied them, during the coassembly as water was added to the polymer/LaF3/THF/ dioxane mixture. © 2009 American Chemical Society.

  1. Fabrication of Octahedral Gold Nanoparticle embedded Polymer Pattern based on Electron Irradiation and Thermal Treatment

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yong Nam; Lee, Hyeok Moo; Cho, Sung Oh [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)


    Noble metal nanoparticles (NPs) such as gold (Au), silver, and copper have been a hot research issue due to their unique optical, electronic, and catalytic properties. On account of the size- and shape- dependent properties of the noble metal NPs, most researches are concentrated on tailoring sizes and shapes of the noble metal NPs. In particular, noble metal NPs with Platonic shapes such as tetrahedron, cube, octahedron, dodecahedron, and icosahedron have significant impact on a variety of applications including surface-enhancement spectroscopy, biochemical sensing, and nanodevice fabrication because sharp corners of the metals lead to high local electric-field enhancement. In addition, patterning or controlled assembly of noble metal NPs is indispensible for biological sensors, micro-/nano-electronic devices, photonic and photovoltaic devices, and surface-enhanced Raman scattering (SERS)-active substrates. Although Platonic noble metal NPs with well defined sizes have been intensively studied, patterning of Platonic noble metal NPs has been rarely demonstrated. Here, we present a strategy to fabricate patterned Au nano-octahedra embedded polymer films by selectively irradiating an electron beam onto HAuCl{sub 4}-loadaed poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) block copolymer (BCP) precursor films followed by thermal treatment. The BCP plays a important role for the patterning of the precursor film due to a cross-linking behavior under electron irradiation

  2. Enhanced stability of low fouling zwitterionic polymer brushes in seawater with diblock architecture. (United States)

    Quintana, Robert; Gosa, Maria; Jańczewski, Dominik; Kutnyanszky, Edit; Vancso, G Julius


    The successful implementation of zwitterionic polymeric brushes as antifouling materials for marine applications is conditioned by the stability of the polymer chain and the brush-anchoring segment in seawater. Here we demonstrate that robust, antifouling, hydrophilic polysulfobetaine-based brushes with diblock architecture can be fabricated by atom-transfer radical polymerization (ATRP) using initiator-modified surfaces. Sequential living-type polymerization of hydrophobic styrene or methyl methacrylate and commercially available hydrophilic sulfobetaine methacrylamide (SBMAm) monomer is employed. Stability enhancement is accomplished by protecting the siloxane anchoring bond of brushes on the substrate, grafted from silicon oxide surfaces. The degradation of unprotected PSBMAm brushes is clearly evident after a 3 month immersion challenge in sterilized artificial seawater. Ellipsometry and atomic force microscopy (AFM) measurements are used to follow changes in coating thickness and surface morphology. Comparative stability results indicate that surface-tethered poly(methyl methacrylate) and polystyrene hydrophobic blocks substantially improve the stability of zwitterionic brushes in an artificial marine environment. In addition, differences between the hydration of zwitterionic brushes in fresh and salt water are discussed to provide a better understanding of hydration and degradation processes with the benefit of improved design of polyzwitterionic coatings.

  3. Polymer Nanocomposites

    Indian Academy of Sciences (India)

    The synthesis of polymer nanocomposites is an integral aspect of polymer nanotechnology. By inserting the nano- metric inorganic compounds, the properties of polymers improve and hence this has a lot of applications depending upon the inorganic material present in the polymers. Sol- vent casting is one of the easiest ...

  4. Genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food

    Directory of Open Access Journals (Sweden)

    Makoto Nakai


    Full Text Available Here, we conducted in vitro genotoxicity tests to evaluate the genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food. Styrene oligomers were extracted with acetone and the extract was subjected to the Ames test (OECD test guideline No. 471 and the in vitro chromosomal aberration test (OECD test guideline No. 473 under good laboratory practice conditions. The concentrations of styrene dimers and trimers in the concentrated extract were 540 and 13,431 ppm, respectively. Extraction with acetone provided markedly higher concentrations of styrene oligomers compared with extraction with 50% ethanol aqueous solution, which is the food simulant currently recommended for use in safety assessments of polystyrene by both the United States Food and Drug Administration and the European Food Safety Authority. And these high concentrations of styrene dimers and trimers were utilized for the evaluation of genotoxicity in vitro. Ames tests using five bacterial tester strains were negative both in the presence or absence of metabolic activation. The in vitro chromosomal aberration test using Chinese hamster lung cells (CHL/IU was also negative. Together, these results suggest that the risk of the genotoxicity of styrene oligomers that migrate from polystyrene food packaging into food is very low.

  5. Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaomeng [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Luan Shifang, E-mail: [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yang Huawei; Shi Hengchong; Zhao Jie; Jin Jing [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yin Jinghua, E-mail: [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Stagnaro, Paola [Istituto per Io Studio delle Macromolecole, Consiglio Nazionale delle Ricerche, Via de Marini 6, 16149 Genova (Italy)


    Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.

  6. Nanostructured polymer membranes for proton conduction (United States)

    Balsara, Nitash Pervez; Park, Moon Jeong


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

  7. Reinforcement effect of soy protein/carbohydrate ratio in styrene-butadiene polymer (United States)

    Soy protein and carbohydrate at different ratios were blended with latex to form composites. The variation of protein to carbohydrate ratio has a sifnificant effect on the composite properties and the results from dynamic mechanical method showed a substantial reinforcement effect. The composites ...

  8. Delocalization in polymer models

    CERN Document Server

    Jitomirskaya, S Yu; Stolz, G


    A polymer model is a one-dimensional Schroedinger operator composed of two finite building blocks. If the two associated transfer matrices commute, the corresponding energy is called critical. Such critical energies appear in physical models, an example being the widely studied random dimer model. Although the random models are known to have pure-point spectrum with exponentially localized eigenstates for almost every configuration of the polymers, the spreading of an initially localized wave packet is here proven to be at least diffusive for every configuration.

  9. Styrene-spaced copolymers including anthraquinone and β-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions. (United States)

    Megiatto, Jackson D; Cazeils, Emmanuel; Ham-Pichavant, Frédérique; Grelier, Stéphane; Gardrat, Christian; Castellan, Alain


    A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

  10. Biodegradable Polymers

    Directory of Open Access Journals (Sweden)

    Isabelle Vroman


    Full Text Available Biodegradable materials are used in packaging, agriculture, medicine and other areas. In recent years there has been an increase in interest in biodegradable polymers. Two classes of biodegradable polymers can be distinguished: synthetic or natural polymers. There are polymers produced from feedstocks derived either from petroleum resources (non renewable resources or from biological resources (renewable resources. In general natural polymers offer fewer advantages than synthetic polymers. The following review presents an overview of the different biodegradable polymers that are currently being used and their properties, as well as new developments in their synthesis and applications.

  11. Polymer electronics

    CERN Document Server

    Hsin-Fei, Meng


    Polymer semiconductor is the only semiconductor that can be processed in solution. Electronics made by these flexible materials have many advantages such as large-area solution process, low cost, and high performance. Researchers and companies are increasingly dedicating time and money in polymer electronics. This book focuses on the fundamental materials and device physics of polymer electronics. It describes polymer light-emitting diodes, polymer field-effect transistors, organic vertical transistors, polymer solar cells, and many applications based on polymer electronics. The book also disc

  12. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

    Energy Technology Data Exchange (ETDEWEB)

    Liedel, Clemens [RWTH Aachen University; Schindler, Kerstin [RWTH Aachen University; Pavan, Mariela J. [Hebrew University of Jerusalem; Lewin, Christian [RWTH Aachen University; Pester, Christian W [ORNL; Ruppel, Markus A [ORNL; Urban, Volker S [ORNL; Shenhar, Roy [Hebrew University of Jerusalem; Boker, Alexander [RWTH Aachen University


    External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

  13. Effect of modified graphene and microwave irradiation on the mechanical and thermal properties of poly(styrene-co-methyl methacrylate)/graphene nanocomposites

    KAUST Repository

    Zubair, Mukarram


    The effect of modified graphene (MG) and microwave irradiation on the interaction between graphene (G) and poly(styrene-co-methyl meth acrylate) [P(S-co-MMA)] polymer matrix has been studied in this article. Modification of graphene was performed using nitric acid. P(S-co-MMA) polymer was blended via melt blending with pristine and MG. The resultant nanocomposites were irradiated under microwave at three different time intervals (5, 10, and 20 min). Compared to pristine graphene, MG showed improved interaction with P(S-co-MMA) polymer (P) after melt mixing and microwave irradiation. The mechanism of improved dispersion and interaction of modified graphene with P(S-co-MMA) polymer matrix during melt mixing and microwave irradiation is due to the presence of oxygen functionalities on the surface of MG as confirmed from Fourier transform infrared spectroscopy. The formation of defects on modified graphene and free radicals on P(S-co-MMA) polymer chains after irradiation as explained by Raman spectroscopy and X-Ray diffraction studies. The nanocomposites with 0.1 wt% G and MG have shown a 26% and 38% increase in storage modulus. After irradiation (10 min), the storage modulus further improved to 11.9% and 27.6% of nanocomposites. The glass transition temperature of nanocomposites also improved considerably after melt mixing and microwave irradiation (but only for polymer MG nanocomposite). However, at higher irradiation time (20 min), degradation of polymer nanocomposites occurred. State of creation of crosslink network after 10 min of irradiation and degradation after 20 min of irradiation of nanocomposites was confirmed from SEM studies. Copyright © 2014 John Wiley & Sons, Ltd.

  14. Study of Polymer Material Aging by Laser Mass Spectrometry, UV-Visible Spectroscopy, and Environmental Scanning Electron Microscopy


    Junien Exposito; Claude Becker; David Ruch; Frédéric Aubriet


    Dyed natural rubber (NR) and styrene butadiene rubber (SBR), designed for outdoor applications, were exposed to an accelerated artificial aging in xenon light. The aging results in the deterioration of the exposed surface material properties. The ability of dyed polymers to withstand prolonged sunlight exposure without fading or undergoing any physical deterioration is largely determined not only by the photochemical characteristics of the absorbing dyestuff itself but also by the polymer str...

  15. Mechanisms of polymer-templated nanoparticle synthesis: contrasting ZnS and Au


    Podhorska, L; Delcassian, D; Goode, AE; Agyei, M; Mccomb, DW; Ryan, MP; Dunlop, IE


    We combine solution small-angle X-ray scattering (SAXS) and high-resolution analytical transmission electron microscopy (ATEM) to gain a full mechanistic understanding of substructure formation in nanoparticles templated by block copolymer reverse micelles, specifically poly(styrene)-block-poly(2-vinyl pyridine). We report a novel substructure for micelle-templated ZnS nanoparticles, in which small crystallites (~4 nm) exist within a larger (~20 nm) amorphous organic-inorganic hybrid matrix. ...

  16. Fatigue Characteristics of 3D Printed Acrylonitrile Butadiene Styrene (ABS) (United States)

    Padzi, M. M.; Bazin, M. M.; Muhamad, W. M. W.


    Recently, the use of 3D printer technology has become significant to industries, especially when involving the new product development. 3D printing is a technology, which produces the 3D product or prototype using a layer-by-layer technique. However, there becomes less research on the mechanical performance of the 3D printed component. In the present work, fatigue characteristics of 3D printed specimen have been studied. Acrylonitrile butadiene styrene (ABS) has been chosen as a material research due to its wide applications. Two types of specimen used, which is the 3D printing and moulding specimens. Fused deposition modelling (FDM) technique was used to produce the specimens. The dog bone shape part was produced based on ASTM D638 standard and the tensile test has been carried out to get the mechanical properties. Fatigue test was carried out at 40%, 60% and 80% of the tensile strength. The moulded part shows higher fatigue cycles compared to 3D printed part for all loading percentages. Fatigue lives for 40%, 60% and 80%, were 911, 2645 and 26948 cycles, respectively. The results indicated that 3D printed part has a lower fatigue life, which may not suitable for industrial applications. However, the 3D printed part could be improved by using various parameters and may be introduced in low strength application.

  17. Polymers at liquid-liquid interfaces: Photophysics and photoredox chemistry. Progress report, April 1, 1991--March 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Webber, S.E.


    This report consists of three sections: study of triplet state electron transfer from polymer-bound anthracene and pyrene chromophores, adsorption of alternating block and comb polymers onto polymer surfaces, and discussion of transient absorption systems.

  18. Solid-phase peptide synthesis of endothelin receptor antagonists on novel flexible, styrene-acryloyloxyhydroxypropyl methacrylate-tripropyleneglycol diacrylate [SAT] resin. (United States)

    Siyad, M A; Nair, Arun S V; Kumar, G S Vinod


    Novel cross-linked polymeric support by the copolymerization of styrene and 3-(acryloyloxy)-2-hydroxypropyl methacrylate with Tri(propyleneglycol) diacryalte (SAT) for solid-phase peptide synthesis is presented here. The synthesis of SAT is based on the cross-linking of 3-(acryloyloxy)-2-hydroxypropyl methacrylate with styrene by free-radical suspension polymerization, consisting of an ester and a secondary hydroxyl group. An additional cross-linker tri(propyleneglycol) diacryalte provides a hydrophilic environment throughout the resin, which will enhance the physicochemical properties of the resin toward organic synthesis. The resins were synthesized in various cross-linking densities to check the swelling property, mechanical stability, and functional loading capacity. The resin was characterized by the IR, (13)C NMR, and SEM techniques. The extent of swelling properties of the polymer of different cross-linking densities were studied and compared with Merrifield resin and TentaGel. To demonstrate the efficiency of SAT support was proved by synthesizing the challenging peptide sequence of acyl carrier protein (ACP) and compared with commercially available Merrifield resin. It was further tested by synthesizing endothelial receptor antagonist peptides using SAT resin and compared with commercially available TentaGel resin. The standard Fmoc strategy was adopted for peptide synthesis and was characterized by MALDI-TOF MS and analyzed the purity of peptides by HPLC.

  19. Nanoparticle Network Formation in Nanostructured and Disordered Block Copolymer Matrices

    Directory of Open Access Journals (Sweden)

    Khan Saad


    Full Text Available Abstract Incorporation of nanoparticles composed of surface-functionalized fumed silica (FS or native colloidal silica (CS into a nanostructured block copolymer yields hybrid nanocomposites whose mechanical properties can be tuned by nanoparticle concentration and surface chemistry. In this work, dynamic rheology is used to probe the frequency and thermal responses of nanocomposites composed of a symmetric poly(styrene-b-methyl methacrylate (SM diblock copolymer and varying in nanoparticle concentration and surface functionality. At sufficiently high loading levels, FS nanoparticle aggregates establish a load-bearing colloidal network within the copolymer matrix. Transmission electron microscopy images reveal the morphological characteristics of the nanocomposites under these conditions.

  20. Protein and bacterial interactions with nanostructured polymer coatings. (United States)

    Juvonen, Helka; Oja, Terhi; Määttänen, Anni; Sarfraz, Jawad; Rosqvist, Emil; Riihimäki, Tiina A; Toivakka, Martti; Kulomaa, Markku; Vuorela, Pia; Fallarero, Adyary; Peltonen, Jouko; Ihalainen, Petri


    Adsorption of proteins and adhesion of bacteria to a surface is affected by chemical and physical interactions. In this study, polymer coatings and their ability to adsorb avidin and Staphylococcus aureus were investigated. The surface chemistry and topography of the polymer coatings was modified by changing the weight ratio of the hydrophobic polystyrene (PS) and the hydrophilic acrylonitrile butadiene styrene (ABS) components in the polymer blend. Avidin adsorbed less to the ABS phase compared with the PS phase. The side-on orientation of avidin on the ABS surface, however, resulted in a higher specific binding of biotinylated bovine serum albumin. Steric effects and hydrophobic protein-surface interactions decreased the activity of avidin on the PS phase. The increased hydrophobicity and roughness of the polymer coatings enhanced the adhesion of S. aureus. The avidin-coated latex surface with 55% relative surface coverage of the PS phase showed anti-microbial behavior. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Binary and ternary LLE data of the system (ethylbenzene + styrene + 1-ethyl-3-methylimidazolium thiocyanate) and binary VLE data of the system (styrene + 1-ethyl-3-methylimidazolium thiocyanate)

    NARCIS (Netherlands)

    Jongmans, Mark; Schuur, Boelo; de Haan, A.B.


    The distillation of close boiling mixtures may be improved by adding a proper affinity solvent, and thereby creating an extractive distillation process. An example of a close boiling mixture that may be separated by extractive distillation is the mixture ethylbenzene/styrene. The ionic liquid

  2. In Situ Investigation of the Adsorption of Styrene Phosphonic Acid on Cassiterite (110) Surface by Molecular Modeling

    National Research Council Canada - National Science Library

    Guichen Gong; Yuexin Han; Jie Liu; Yimin Zhu; Yanfeng Li; Shuai Yuan


    The flotation, adsorption and bonding mechanisms of styrene phosphonic acid (SPA) to cassiterite were studied using microflotation tests, zeta potential measurements, solution chemistry analysis and density functional theory...

  3. Occupational exposure to styrene in the fibreglass reinforced plastic industry: comparison between two different manufacturing processes. (United States)

    Tranfo, Giovanna; Gherardi, Monica; Paci, E; Gatto, Mariapia; Gordiani, A; Caporossi, Lidia; Capanna, Silvia; Sisto, Renata; Papaleo, B; Fiumalbi, Carla; Garofani, Patrizia


    Styrene is used in manufacturing fiberglass reinforced plastics: and occupational exposure was related to neurotoxicology and genotoxicity. The sum of the metabolites mandelic and phenylglyoxylic acids is the ACGIH biomarker for occupational exposure with a BEI of 400 mg/g of creatinine in end shift urine corresponding to a airborne styrene concentration of 85 mg/m3. There are two main molding processes, open and closed, the last more effective at controlling worker's styrene exposure. To compare the open molding process to the compression of fiber reinforced resin foils, a kind of closed molding, monitoring the styrene exposure of workers in two production sites (A and B). Environmental Monitoring was carried out by Radiello samplers and Biological Monitoring by means of the determination of MA and PGA with HPLC/MS/MS in 10 workers at Site A and 14 at Site B. The median values for styrene exposure resulted 31.1 mg/m3 for Site A and 24.4 mg/m for Site B, while the medians for the sum of the two metabolites in the end shift urine were 86.7 e 33.8 mg/g creatinine respectively. There is a significant linear correlation between personal styrene exposure and the excretion of styrene metabolites (R = 0.74). As expected the exposure markers of the workers of the two production sites resulted higher in the open process. The analytical results of both environmental and biological monitoring were all below the occupational exposure limits, confirming the efficacy of the protective devices.

  4. Solution Processing - Rodlike Polymers (United States)


    side it necessary and identify by block number) Para-ordered Polymers High Modulus Fibers and Films Polybenzobisoxazoles Polybenzobisthiazoles 20...considerations important in solution processing are considered, with special emphasis on the dry-jet wet spinning process used to form fibers . Pertinent...Company, Summit, N.J. iii TABLE OF CONTENTS 1. INTRODUCTION ................ .......................... .. 1 2. REMARKS ON DRY-JET WET SPUN FIBER

  5. High temperature chemically resistant polymer concrete (United States)

    Sugama, T.; Kukacka, L.E.

    High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

  6. Preparation of polymer-modified electrodes: A literature and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Jayanta, Pat Siripastr [Stony Brook Univ., NY (United States); Ishida, Takanobu [Stony Brook Univ., NY (United States)


    A literature review is presented on the field of polymer modified electrodes which can be electrochemically generated. It is suggested that a possible application of these polymer modified electrodes is as a regeneratable catalysis packing material for use in couter-current exchange columns. Secondly, there is a presentation of experimental results dealing with possible electrode modification using difluoro- and dimethyl- phenols and fluorinated derivatives of styrene, benzoquinone and hydroquinone. It appears that dimethylphenol shows the most potential of the monomers experimentally tested in providing a stable polymer modified electrode surface.

  7. Preparation of polymer-modified electrodes: A literature and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Jayanta, P.S.; Ishida, Takanobu.


    A literature review is presented on the field of polymer modified electrodes which can be electrochemically generated. It is suggested that a possible application of these polymer modified electrodes is as a regeneratable catalysis packing material for use in couter-current exchange columns. Secondly, there is a presentation of experimental results dealing with possible electrode modification using difluoro- and dimethyl- phenols and fluorinated derivatives of styrene, benzoquinone and hydroquinone. It appears that dimethylphenol shows the most potential of the monomers experimentally tested in providing a stable polymer modified electrode surface. 170 refs., 31 figs., 1 tab.

  8. Nanostructured silicate polymer concrete

    Directory of Open Access Journals (Sweden)

    Figovskiy Oleg L'vovich


    Full Text Available It has been known that acid-resistant concretes on the liquid glass basis have high porosity (up to 18~20 %, low strength and insufficient water resistance. Significant increasing of silicate matrix strength and density was carried out by incorporation of special liquid organic alkali-soluble silicate additives, which block superficial pores and reduce concrete shrinkage deformation. It was demonstrated that introduction of tetrafurfuryloxisilane additive sharply increases strength, durability and shock resistance of silicate polymer concrete in aggressive media. The experiments showed, that the strength and density of silicate polymer concrete increase in case of decreasing liquid glass content. The authors obtained optimal content of silicate polymer concrete, which possesses increased strength, durability, density and crack-resistance. Diffusive permeability of concrete and its chemical resistance has been investigated in various corroding media.

  9. Cationic surfactants/copoly(styrene oxide-ethylene oxide) systems: A physico-chemical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Taboada, Pablo [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)], E-mail:; Castro, Emilio [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain); Barbosa, Silvia [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain); Mosquera, Victor [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)


    The interactions between the diblock copolymer S{sub 15}E{sub 63} and the surfactants dodecyltrimethylammonium (DoTAB) and hexadecyltrimethylammoniun (CTAB) bromides have been investigated by dynamic light scattering, transmission electron microscopy and isothermal titration calorimetry. The surfactants with the same headgroup differentiate in their chain length. At 20 deg C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.3 nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The different copolymer/surfactant systems have been studied at a constant copolymer concentration of 2.5 g dm{sup -3} and in a vast range of surfactant concentration, from 5.0 x 10{sup -6} up to 0.1 M. When DoTAB is added to the block copolymer solution, no important variations are observed in the apparent hydrodynamic radius up to a surfactant concentration of {approx}10{sup -2} M, for which this magnitude starts decreasing abruptly as a consequence of disruption of the copolymer micelles due to surfactant binding. This phenomenon is also observed for CTAB but at much lower concentrations ({approx}10{sup -5} M). This decrease is associated to repulsive electrostatic interactions between surfactant headgroups in the micelle. Complete disruption of the mixed aggregates occurs neither for DoTAB nor CTAB in the measured concentration range. Transmission electron microscopy has confirmed this behaviour. Titration calorimetric data of micellised DoTAB present a plateau region indicating no interaction between the copolymer and the surfactant at low surfactant concentrations, followed by an exothermic decrease as a consequence of starting copolymer micelle disruption. For CTAB, an endothermic maximum points out the existence of interactions between copolymer micelles and this surfactant. This maximum is followed by a steep decrease which reflects the disruption of the mixed surfactant/copolymer micelles up

  10. Modified hydrogenated PBLH copolymer synthesis with styrene for proton exchange membranes fuel cell application; Derivados de PBLH hidrogenado na sintese de copolimeros com estireno, para a producao de membranas cationicas para celulas a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Ferraz, Fernando A.; Oliveira, Angelo R.S.; Rodrigues, Maraiza F.; Groetzner, Mariana B.; Cesar-Oliveira, Maria Aparecida F. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica. Lab. de Polimeros Sinteticos (LABPOL)]. E-mails:;;;;; Cantao, Mauricio P. [Instituto de Tecnologia para o Desenvolvimento (LACTEC), Curitiba, PR (Brazil)]. E-mail:


    Polymers used as electrolyte in fuel cells are expected to have functional groups in their structure which are responsible for proton conductivity. Since the use of hydroxylated liquid polybutadiene (PBLH) has not been mentioned in the literature as an ion exchange membrane for fuel cell application (PEMFC), and its structure can be modified for a later sulfonation, it has been studied. In this work, PBLH was modified through a hydrogenation reaction. Furthermore, hydrogenated polymeric esters were obtained by esterification and transesterification reactions (PBLH- estearate and PBLH- methacrylate). Reacting the PBLH methacrylate with styrene, it was generated a copolymer with appropriated structure for sulfonation, justifying researches for fuel cell. (author)


    NARCIS (Netherlands)

    Morichere, D; Malliaras, G.G; Krasnikov, V.V.; Bolink, H.J; Hadziioannou, G

    The use of polymers as photorefractive materials offers many advantages : flexibility in synthesis, doping, processing and low cost. The required functionalities responsible for photorefractivity, namely charge generation, transport, trapping and linear electrooptic effect are given in the polymer

  12. Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE). (United States)

    Vilaplana, Francisco; Ribes-Greus, Amparo; Karlsson, Sigbritt


    A fast method for the determination of brominated flame retardants (BFRs) in styrenic polymers using microwave-assisted extraction (MAE) and liquid chromatography with UV detection (HPLC-UV) was developed. Different extraction parameters (extraction temperature and time, type of solvent, particle size) were first optimised for standard high-impact polystyrene (HIPS) samples containing known amounts of tetrabromobisphenol A (TBBPA) and decabromodiphenyl ether (Deca-BDE). Complete extraction of TBBPA was achieved using a combination of polar/non-polar solvent system (isopropanol/n-hexane) and high extraction temperatures (130 degrees C). Lower extraction yields were, however, obtained for Deca-BDE, due to its high molecular weight and its non-polar nature. The developed method was successfully applied to the screening of BFRs in standard plastic samples from waste electrical and electronic equipment (WEEE); TBBPA could be fully recovered, and Deca-BDE could be identified, together with minor order polybrominated diphenyl ether (PBDE) congeners.

  13. Controlled release from recombinant polymers. (United States)

    Price, Robert; Poursaid, Azadeh; Ghandehari, Hamidreza


    Recombinant polymers provide a high degree of molecular definition for correlating structure with function in controlled release. The wide array of amino acids available as building blocks for these materials lend many advantages including biorecognition, biodegradability, potential biocompatibility, and control over mechanical properties among other attributes. Genetic engineering and DNA manipulation techniques enable the optimization of structure for precise control over spatial and temporal release. Unlike the majority of chemical synthetic strategies used, recombinant DNA technology has allowed for the production of monodisperse polymers with specifically defined sequences. Several classes of recombinant polymers have been used for controlled drug delivery. These include, but are not limited to, elastin-like, silk-like, and silk-elastinlike proteins, as well as emerging cationic polymers for gene delivery. In this article, progress and prospects of recombinant polymers used in controlled release will be reviewed. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Controlled Release from Recombinant Polymers (United States)

    Price, Robert; Poursaid, Azadeh; Ghandehari, Hamidreza


    Recombinant polymers provide a high degree of molecular definition for correlating structure with function in controlled release. The wide array of amino acids available as building blocks for these materials lend many advantages including biorecognition, biodegradability, potential biocompatibility, and control over mechanical properties among other attributes. Genetic engineering and DNA manipulation techniques enable the optimization of structure for precise control over spatial and temporal release. Unlike the majority of chemical synthetic strategies used, recombinant DNA technology has allowed for the production of monodisperse polymers with specifically defined sequences. Several classes of recombinant polymers have been used for controlled drug delivery. These include, but are not limited to, elastin-like, silk-like, and silk-elastinlike proteins, as well as emerging cationic polymers for gene delivery. In this article, progress and prospects of recombinant polymers used in controlled release will be reviewed. PMID:24956486

  15. Single-strand breaks, chromosome aberrations, sister-chromatid exchanges, and micronuclei in blood lymphocytes of workers exposed to styrene during the production of reinforced plastics

    Energy Technology Data Exchange (ETDEWEB)

    Maeki-Paakkanen, J.W.; Walles, S.; Osterman-Golkar, S.; Norppa, H. (Institute of Occupational Health, Helsinki (Finland))


    Chromosome aberrations (CA), micronuclei (MN, cytokinesis-block (CB) method), and sister-chromatid exchanges (SCE) were analysed in blood lymphocytes of 17 workers and 17 control subjects. The mean urinary mandelic acid level (average 9.4 mmol/l) and styrene glycol in blood (average 2.5 mumol/l) implied exposure to about 300 mg/m3 of styrene in the plant. The number of CA was significantly higher in non-smoking workers compared with nonsmoking controls. A significant correlation was observed between duration of exposure and individual CA level of all workers. No significant effects were observed in MN or SCE. Single-strand breaks (SSB) in DNA of isolated lymphocytes were studied in nine of the workers and eight of the controls by the DNA-unwinding technique. The results showed an increase in SSB among the exposed workers. The present findings support earlier reports on the increase of structural CA in blood lymphocytes of workers in the reinforced plastic industry, and also show that SSBs are elevated in such workers.

  16. Two polyoxometalate-based coordination polymers constructed from Mn(II)-4,4'-bipyridine-N,N'-dioxide building blocks and Keggin-type clusters: Syntheses, crystal structures and spectral properties. (United States)

    Bai, Yan; Li, Meng-Meng; Huang-Fu, You-Jing; Dang, Dong-Bin


    Two polyoxometalate-based coordination polymers {[Mn2(dpdo)4(H2O)6](GeMo12O40)(H2O)4}n (1) and {[Mn2(dpdo)4(H2O)6](GeW12O40)(H2O)3}n (2) (dpdo=4,4'-bipyridine-N,N'-dioxide) have been synthesized and characterized by IR, elemental analysis, XRPD, TG technique and X-ray crystallography. The polymers 1 and 2 are basically isostructural and feature a 3D supramolecular framework decorated with Keggin-type polyanion clusters based on one-dimension polymeric chains, which formed through the coordination interaction of Mn(II) and dpdo. The luminescent properties of the polymers were investigated in the solid state at room temperature. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Gyroid nanoporous scaffold for conductive polymers

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Schulte, Lars; Zhang, Weimin


    Conductive nanoporous polymers with interconnected large surface area have been prepared by depositing polypyrrole onto nanocavity walls of nanoporous 1,2-polybutadiene films with gyroid morphology. Vapor phase polymerization of pyrrole was used to generate ultrathin films and prevent pore blocking....... The resulting nanoporous polymers exhibited a promising electroactivity....

  18. The filler-rubber interface in styrene butadiene nanocomposites with anisotropic silica particles: morphology and dynamic properties. (United States)

    Tadiello, L; D'Arienzo, M; Di Credico, B; Hanel, T; Matejka, L; Mauri, M; Morazzoni, F; Simonutti, R; Spirkova, M; Scotti, R


    Silica-styrene butadiene rubber (SBR) nanocomposites were prepared by using shape-controlled spherical and rod-like silica nanoparticles (NPs) with different aspect ratios (AR = 1-5), obtained by a sol-gel route assisted by a structure directing agent. The nanocomposites were used as models to study the influence of the particle shape on the formation of nanoscale immobilized rubber at the silica-rubber interface and its effect on the dynamic-mechanical behavior. TEM and AFM tapping mode analyses of nanocomposites demonstrated that the silica particles are surrounded by a rubber layer immobilized at the particle surface. The spherical filler showed small contact zones between neighboring particles in contact with thin rubber layers, while anisotropic particles (AR > 2) formed domains of rods preferentially aligned along the main axis. A detailed analysis of the polymer chain mobility by different time domain nuclear magnetic resonance (TD-NMR) techniques evidenced a population of rigid rubber chains surrounding particles, whose amount increases with the particle anisotropy, even in the absence of significant differences in terms of chemical crosslinking. Dynamic measurements demonstrate that rod-like particles induce stronger reinforcement of rubber, increasing with the AR. This was related to the self-alignment of the anisotropic silica particles in domains able to immobilize rubber.

  19. Protons conductive membranes from sulfonated styrenic copolymers; Membranas conductoras de protons a partir de copolimeros estirenicos sulfonados

    Energy Technology Data Exchange (ETDEWEB)

    Brum, F.J.B.; Silva, M.A.G.; Amico, S.C.; Malfatti, C.F.; Forte, M.M.C. [Universidade Federal do Rio Grande do Sul (EE/UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia], e-mail:; Vargas, J.V.C. [Universidade Federal do Parana (DEM/UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica


    Fuel cells working with polymeric electrolyte known as Proton Exchange Membrane Fuel Cell (PEMFC) have become a promising source for energy generation since they can produce high density electric current in an effective way. In this work, a polymeric precursor based on sulfonated styrenic copolymer (RHS) was used with the aim of producing ion-exchange membranes thermally stable at 80 deg C and over. Films of RHS and poly(vinylalcohol) (PVA) mixtures with different polyelectrolyte content were prepared, using glutaraldehyde as a crosslinking agent and antimonic acid. The films or membranes were analyzed by infrared and electrochemical impedance spectroscopy, differential scanning calorimetry, thermogravimetry and water absorption content. The impedance studies showed that the ionic conductivity of the RHS/PVA membranes was highly dependent on the electrolyte polymer in a way that the higher the content, the higher the membrane ionic conductivity. The RHS66{sub G}1 showed ionic conductivity similar to the Nafion membrane analyzed at the same conditions. (author)

  20. Stepwise swelling of a thin film of lamellae-forming poly(styrene-b- butadiene) in cyclohexane vapor

    KAUST Repository

    Di, Zhenyu


    We investigated the swelling of a thin film of lamellae-forming poly(styrene-b-butadiene) in cyclohexane vapor. The vapor pressure and thus the degree of swelling of the film are increased in a stepwise manner using a custom-built sample cell. The resulting structural changes during and after each step were followed in situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). During the first step, the lamellar thickness increases strongly, before it decreases again. At the same time, the full width at half-maximum (FWHM) of the diffuse Bragg reflection along the film normal has a sharp maximum. These observations point to the formation of new lamellae. During the subsequent swelling steps, the lamellar thickness overshoots only weakly. The behavior thus resembles qualitatively our previous results on a similar thin film during swelling in saturated vapor of cyclohexane; however, it deviates from earlier theoretical predictions. We propose a theory that is quantitatively correct for the description of the dependence of the lamellar thickness on the polymer volume fraction in the late stage of the swelling steps. © 2012 American Chemical Society.

  1. Preparation and self-sterilizing properties of Ag@TiO2-styrene-acrylic complex coatings. (United States)

    Zhou, Xiang-dong; Chen, Feng; Yang, Jin-tao; Yan, Xiao-hui; Zhong, Ming-qiang


    In this study, we report a simple and cost-effective method for self-sterilized complex coatings obtained by Ag@TiO2 particle incorporation into styrene-acrylic latex. The Ag@TiO2 particles were prepared via a coupling agent modification process. The composite latices characterized by transmission electron microscopy (TEM) study were highly homogeneous at the nanometric scale, and the Ag@TiO2 particles were well dispersed and exhibited an intimate contact between both the organic and inorganic components. The Ag@TiO2 nanoparticles significantly enhanced the absorption in the visible region and engendered a good heat-insulating effect of the complex coatings. Moreover, the Ag@TiO2 nanoparticle incorporation into this polymer matrix renders self-sterilized nanocomposite materials upon light excitation, which are tested against Escherichia coli and Staphylococcus aureus. The complex coatings display an impressive performance in the killing of all micro-organisms with a maximum for a Ag@TiO2 loading concentration of 2-5 wt.%. The weathering endurance of the complex coating was also measured. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Continuous Preparation of Hollow Polymeric Nanocapsules Using Self-Assembly and a Photo-Crosslinking Process of an Amphiphilic Block Copolymer

    Directory of Open Access Journals (Sweden)

    Xuan Don Nguyen


    Full Text Available This paper presents a fabrication method of hollow polymeric nanocapsules (HPNCs. The HPNCs were examined to reduce light trapping in an organic light emitting diodes (OLED device by increasing the refractive index contrast. They were continuously fabricated by the sequential process of self-assembly and photo-crosslinking of an amphiphilic block copolymer of SBR-b-PEGMA, poly(styrene-r-butadiene-b-poly(poly(ethylene glycol methyl ether methacrylate in a flow-focusing microfluidic device. After the photo-crosslinking process, the produced HPNCs have a higher resistance to water and organic solvents, which is applicable to the fabrication process of optical devices. The morphology and hollow structure of the produced nanocapsules were determined by transmission electron microscopy (TEM, scanning electron microscopy (SEM, and atomic force microscopy (AFM. Also, their size control was examined by varying the ratio of inlet flow rates and the morphological difference was studied by changing the polymer concentration. The size was measured by dynamic light scattering (DLS. The refractive index of the layer with and without the HPNCs was measured, and a lower refractive index was obtained in the HPNCs-dispersed layer. In future work, the light extraction efficiency of the HPNCs-dispersed OLED will be examined.

  3. Evaluation the effect of using polymers on the performance of wearing asphalt mixture

    Directory of Open Access Journals (Sweden)

    Yasir Mohammed Jebur


    Full Text Available In Iraq , the increasing in number of vehicles and trucks with their heavy traffic loading and under high temperature , a variety of pavement distresses continues to develop affecting the performance and economy of pavement construction. Polymer modified asphalt mixtures have been used to resist the distresses that produced and developed from the applied stresses. Several distresses effect on the performance of HMA. The primary forms of distress are fatigue cracking , rutting , moisture damage and thermal cracking. These distresses reduce the services life of HMA and increase the maintenance costs. The main objective of this research is to find the effect of polymers on the performance of asphalt mixtureby using one asphalt cement grade (40-50 from Al-Daurah refinery with two types of locally available polymers (Low-Density Polyethylene LDPE and Styrene Butadiene Styrene SBS with three percentages for each type. These percent are (1, 3 and 6 % for (LDPE & SBS by weight of asphalt cement. Each type of these polymers is blended with asphalt cement by using the wet process. The experimental work showed that all polymer-modified mixtures have stability and indirect tensile strength higher than the control mixtures. It can be concluded that the addition of (1% LDPE and (3% SBS to asphalt mixtures showed better improvement on the performance properties of pavement modified with these polymers , in which the referred percent represent the optimum percent of concentration for blending polymers .

  4. Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites (United States)

    Bowman, Michelle Kathleen

    Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a

  5. Occupational styrene exposure and acquired dyschromatopsia: A systematic review and meta-analysis. (United States)

    Choi, Ariel R; Braun, Joseph M; Papandonatos, George D; Greenberg, Paul B


    Styrene is a chemical used in the manufacture of plastic-based products worldwide. We systematically reviewed eligible studies of occupational styrene-induced dyschromatopsia, qualitatively synthesizing their findings and estimating the exposure effect through meta-analysis. PubMed, EMBASE, and Web of Science databases were queried for eligible studies. Using a random effects model, we compared measures of dyschromatopsia between exposed and non-exposed workers to calculate the standardized mean difference (Hedges'g). We also assessed between-study heterogeneity and publication bias. Styrene-exposed subjects demonstrated poorer color vision than did the non-exposed (Hedges' g = 0.56; 95%CI: 0.37, 0.76; P dyschromatopsia, suggesting a modest effect size with mild heterogeneity between studies. © 2017 Wiley Periodicals, Inc.

  6. Biosynthesis and characterization of diblock copolymer of p(3-hydroxypropionate)-block-p(4-hydroxybutyrate) from recombinant Escherichia coli

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Linping; Meng, Dechuan


    Poly(4-hydroxybutyrate) (P4HB) is a highly elastic polymer, whereas poly(3-hydroxypropionate) (P3HP) is a polymer with enormous tensile strength. This study aimed to biosynthesize a block copolymer consisting of soft P4HB block with a strong P3HP block to gain unique and excellent material proper...

  7. Measurement of styrene oxide in polystyrenes, estimation of migration to foods, and reaction kinetics and products in food simulants. (United States)

    Philo, M R; Fordham, P J; Damant, A P; Castle, L


    The concentration of styrene-7,8-oxide has been measured in nine base resins and 16 samples of polystyrene articles intended for food contact. The epoxide was not detected in the resins (limit of detection 0.5 mg/kg) but was found in 11 of the 16 packaging samples at up to 2.9 mg/kg. Assuming that the propensity of styrene oxide to migrate is the same as styrene monomer, and using existing survey data for styrene monomer in packaging and foods, the migration levels expected for styrene oxide were calculated. Estimates were from 0.002 to 0.15 microgram/kg styrene oxide in foods. The stability of styrene oxide in the four standard EU food simulants was studied at 40, 100, 150 and 175 degrees C, to establish the transformation products to be expected following migration testing. The half-life at 40 degrees C in distilled water, 15% aqueous ethanol, 3% aqueous acetic acid and olive oil was 15, 23, 2000 hr, respectively. The principal product was the diol from hydrolysis of the epoxide group. Ring opening in aqueous ethanol simulant gave the diol and also the glycol monoethyl ether. It is concluded that this instability of styrene oxide will reduce concentrations in foods, from an already low migration level to even lower levels with the formation of hydrolysis products that are less toxic than the parent epoxide.


    The paper gives results of an investigation of the impact of an ozone generator air cleaner on vapor-phase styrene concentrations in a full-scale indoor air quality test chamber. The time history of the concentrations of styrene and ozone is well predicted by a simulation model u...

  9. Supramolecular Polymers (United States)

    Stupp, S. I.; Keser, M.; Huggins, K. E.; Tew, G.; Li, L. S.; Whitaker, C.


    An interesting target in polymer science is to find pathways to highly regular supramolecular units with dimensions similar to those of high molar mass linear or hyperbranched polymers. These units lack a polymeric backbone but could serve as precursors to shape invariant covalent polymers analogous to folded proteins. We are pursuing access to these polymers with designed molecules programmed to assemble into nanostructures of regular shape and dimension. We have discovered systems of miniaturized triblock copolymers that yield supramolecular polymers. These supramolecular polymers are shaped as mushroom nanostructures, and form materials with interesting surface and optical properties. Molecular modeling indicates that a balance of aggregation and hard core repulsive forces among structural units may be responsible for the formation of these supramolecular polymers.

  10. Polymers under Cylindrical Confinement (United States)

    Russell, Thomas


    Anodized alumina oxide (AAO) membranes offer a unique platform to investigate polymers under confinement. AAO membranes have been prepared where the diameters of the nanopores in the membrane have been varied from 8 to 50 nm by varying the anodization conditions. Capillary force is sufficiently large to draw high molecular weight polymers into the membrane, producing either nanotubes or nanorods. Polymer solutions can also be used place a thin film on the walls of the nanopores, forming nanotubes. With pore diameters less than the radius of gyration, a quantitative understanding of perturbations to chain dynamics due to geometric constraints was examined. We found a weak molecular weight-dependent mobility of polymers confined within AAO nanopores having diameters smaller than the dimension of the chains in the bulk. The measured mobility of polymers in the confined geometry was much higher than the mobility of the unconfined chain. Rayleigh instabilities in thin polymer films confined within nanoporous alumina membranes were also found where periodic undulations on the film surface were found to increase with time, eventually bridging across the cylindrical nanopore, resulting in the formation of polymer nanorods with a periodic array of encapsulated holes. With microphase separated block copolymers, where the characteristic period of the BCP morphology is comparable to the pore diameter, significant deviations from the bulk morphology as revealed by electron tomography. Small angle neutron scattering was also used to investigate the influence of cylindrical confinement on the order-to-disordered transition. This work was done in collaboration with T. J. McCarthy (UMass), K. Shin (Seoul National University), H. Jinnai (Kyoto University), D. Chen, J. Chen, H. Xiang, T. Kim, and P. Dobriyal, and was supported by the DOE, NSF MRSEC, NSF CHM.


    Directory of Open Access Journals (Sweden)

    V. F. Lebedev


    Full Text Available Summary. In the polymerization of butadiene with styrene heat removal is the main factor limiting the output of the cascade reactor. Thus the residence time of the monomers in the reactor exceeds significantly the time necessary to complete the process on the basis of kinetic regularities. To increase the output of the mixture the distribution in the reactor cascade is made. It is necessary to distribute the flow of mixture through the reactor of the cascade to have the resulting polymer of the same viscosity at the outlet of each reactor. The algorithm of distribution of the mixture in the reactor cascade with regard to the synthesis parameters (temperature in the reactor and the feed rate of the mixture, the ratio of the modifier and the initiator in the complex, the number of reactors and a determined dynamic viscosity is developed. In accordance with the developed algorithm the calculation of the velocity of the mixture feed in each reactor of the cascade is made. It is shown that the flow of mixture in each polymerization unit depends on the overall output of the installation and the number of reactors in the cascade. The algorithm for the distribution of the initial mixture in the reactor cascade is developed to provide maximum output of the installation and set the quality of the obtained polymer. To determine the degree of conversion of monomers and temperature conditions of the process of polymerization under the calculated speed of the feed mixture in the first polymerization cascade the basic technological parameters of the polymerization process in real time mode, the calculation using a mathematical model is made. The analysis of the simulation results shows that during the first hour, the concentration of monomers does not exceed of 0.085 mol/l, which corresponds to the degree of conversion of monomer to 99 %, while the temperature in the reactor corresponds to the optimal mode - from 65 to 85 0C.

  12. Solution and solid-state properties of luminescent M-M bond-containing coordination/organometallic polymers using the RNC-M2(dppm)2-CNR building blocks (M = Pd, Pt; R = Aryl, Alkyl). (United States)

    Bérubé, Jean-François; Gagnon, Karl; Fortin, Daniel; Decken, Andreas; Harvey, Pierre D


    Two families of organometallic polymers built upon the bimetallic M2(dppm)2L(2)2+ fragments (M = Pd, Pt; dppm = bis(diphenylphosphino)methane, L = 1,4-diisocyano-2,3,5,6-tetramethylbenzene (diiso), 1,8-diisocyano-p-menthane (dmb), 1-isocyano-2,6-dimethylbenzene, 1-isocyano-4-isopropylbenzene, and tert-butylisocyanide) were synthesized and fully characterized (1H and 31P NMR, X-ray crystallography (model compounds), IR, Raman, chem. anal., TGA, DSC, powder XRD, 31P NMR T1 and NOE, light scattering, and conductivity measurements). Evidence for polymers in the solid state is provided from the swelling of the polymers upon dissolution and the formation of stand-alone films. However, these species become small oligomers when dissolved. The materials are luminescent in the solid state at 298 and 77 K and in PrCN solution at 77 K. These emissions result from triplet 3(d sigma d sigma*) states despite the presence of low-lying pi-pi* MO levels according to DFT calculations for the aryl isocyanide model compounds. The emission band maxima are located between 640 and 750 nm and exhibit lifetimes of 3-6 ns for the Pd species and 3-4 micros for the Pt analogues in PrCN solution at 77 K. No evidence of intramolecular excitonic photoprocesses was found in any of the polymers.

  13. Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide. (United States)

    Leigh, Jessica K; Rajput, Jonathan; Richardson, David E


    An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

  14. Increased frequency of lymphocyte micronuclei in workers producing reinforced polyester resin with low exposure to styrene

    Energy Technology Data Exchange (ETDEWEB)

    Hoegstedt, B.; Akesson, B.; Axell, K.; Gullberg, B.; Mitelman, F.; Pero, R.W.; Skerfving, S.; Welinder, H.


    A new micronucleus method based on the analysis of lymphocytes with preserved cytoplasm revealed an increased frequency of micronuclei in 38 workers employed in a plant producing styrene-modified polyester resin as compared to the frequency in 20 referents (5.9 vs 3.6%). The time-weighted average of the styrene concentration in the workroom air varied between 1 and 36 ppm (mean 13 ppm) during the last year and correlated well to low urinary levels of mandelic acid, which ranged from 9 to 316 mg/g of creatinine (mean 65 mg/g of creatinine).

  15. Impact behaviour of acrylonitrile-butadiene-styrene after temperature and humidity load

    Directory of Open Access Journals (Sweden)

    Hylova Lenka


    Full Text Available This study deals with acrylonitrile-butadiene-styrene (ABS which was subjected the drop-weight test before and after temperature and humidity load. ABS is an engineering plastic and also an important engineering terpolymer, which has butadiene part uniformly distributed through the acrylonitrile-styrene matrix and is commonly used in production of automotive interior components. The injection moulded ABS samples were subjected the penetration test at fall height 100 J before and after temperature and humidity load and the results were subsequently evaluated and discussed. It was found out that ABS after temperature and humidity load has lower impact resistance.

  16. Influence of the Nanoclay Cloisite 20A Incorporation on Properties of Acrylonitrile Butadiene Styrene (ABS) (United States)

    Sales, Jorge N.; Silva, Andressa A.; Valenzuela-Diaz, Francisco R.; Moura, Esperidiana A. B.

    This work aims to study the influence of the nanoclay Cloisite 20A incorporation on mechanical properties of ABS (acrylonitrile butadiene styrene). The incorporation of Cloisite 20A was made in two steps; firstly, a masterbatch was preparated and then, it was incorporated in ABS. The Cloisite 20A masterbatch using 40 % of nanoclay and 60 % of SAN (Styrene Acrylonitrile) was prepared in an adiabatic mill. After that, Cloisite 20A masterbarch at 1 and 5 % (wt) was added in ABS. The resulting nanocomposites were characterized by tensile tests and the correlation between properties was discussed.

  17. Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst


    Betti,Carolina; Badano,Juan; Lederhos,Cecilia; Maccarrone, María; Carrara, Nicolás; Coloma, Fernando; Quiroga, Mónica; Vera, Carlos


    This is a study on the kinetics of the liquid-phase hydrogenation of styrene to ethylbenzene over a catalyst of palladium supported on an inorganic–organic composite. This support has a better mechanical resistance than other commercial supports, e.g. alumina, and yields catalysts with egg-shell structure and a very thin active Pd layer. Catalytic tests were carried out in a batch reactor by varying temperature, total pressure and styrene initial concentration between 353–393 K, 10–30 bar, an...

  18. Electrolytic membrane formation of fluoroalkyl polymer using a UV-radiation-based grafting technique and sulfonation

    Energy Technology Data Exchange (ETDEWEB)

    Shironita, Sayoko; Mizoguchi, Satoko; Umeda, Minoru, E-mail: [Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka 940-2188, Niigata (Japan)


    A sulfonated fluoroalkyl graft polymer (FGP) membrane was prepared as a polymer electrolyte. First, the FGP membrane was grafted with styrene under UV irradiation. The grafted FGP was then sulfonated to functionalize it for proton conductivity. The grafting degree of the membrane increased with increasing grafting time during UV irradiation. The proton conductivity of the membrane increased with increasing grafting degree. The swelling ratio was independent of the grafting time, however, the water uptake increased with increasing grafting degree. Based on these results, it was found that the UV-initiated styrene grafting occurred along the membrane thickness direction. Moreover, the membrane was embedded within the glass fibers of the composite. This composite electrolytic membrane had 1.15 times the proton conductivity of a Nafion 117 membrane.

  19. Differential Scanning Calorimetry (DSC and Thermogravimetric Analysis (TGA of Wood polymer nanocomposites

    Directory of Open Access Journals (Sweden)

    Rahman Md. Rezaur


    Full Text Available This study evaluates the thermal property of clay dispersed Styrene-co-Glycidal Methacrylate impregnated wood polymer nanocomposite (WPNC. The WPNC was characterized by FTIR, TGA and DSC methods. FT-IR result showed that the absorbance of wave number at 1730 cm−1, increased for clay dispersed Styrene-co-Glycidyl Methacrylate wood polymer nanocomposite (ST-co-GMA-clay-WPNC. From TGA, ST-co-GMA-clay-WPNC showed better thermal stability at the temperature below 450oC. The final weights of ST-co-GMA-clay-WPNC and ST-Clay-WPNC, between 420 and 700oC, were significantly less than the raw wood. When the temperature was below 450oC, nanoclay-incorporated surface modified wood composites showed enhanced higher thermal properties compared with those without nanoclay. From DSC, the degradation enthalpy at around 360oC of ST-co-GMA-Clay-WPNC was the highest.

  20. Block copolymer structures in nano-pores (United States)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei


    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  1. Nano-structured polymer composites and process for preparing same (United States)

    Hillmyer, Marc; Chen, Liang


    A process for preparing a polymer composite that includes reacting (a) a multi-functional monomer and (b) a block copolymer comprising (i) a first block and (ii) a second block that includes a functional group capable of reacting with the multi-functional monomer, to form a crosslinked, nano-structured, bi-continuous composite. The composite includes a continuous matrix phase and a second continuous phase comprising the first block of the block copolymer.

  2. Novel Hydrogels from Telechelic Polymers (United States)

    Taribagil, Rajiv R.

    The last two decades have seen telechelic polymers support an increasing number of applications as stabilizers and flow modifiers in fields as varied as pharmaceutics, paints and oil recovery. Mainly consisting of a long hydrophilic block end-capped with hydrophobic blocks, these polymers form gels at modest concentrations, comprising hydrophobic junctions with hydrophilic blocks bridging these junctions. This thesis examines two different types of telechelic polymer hydrogels: concentrated dispersions of telechelic triblock copolymers and dilute solutions of wormlike micelles cross-linked by hydrophobically end-capped polymers. Aqueous gels of telechelic poly(ethylene oxide) (PEO)-based triblock polymers, with homo and hetero combinations of 1,2-polybutadiene (PB) and poly(perfluoropropylene oxide) (PFPO) as hydrophobic end-blocks, were investigated using a combination of cryogenic scanning electron microscopy and small-angle neutron scattering. The PB-b-PEO-b-PB copolymers formed networks of spherical micelles at all concentrations as expected, albeit with significant spatial heterogeneity that diminished with increasing concentration. The PFPO-b-PEO-b-PFPO copolymers also formed networks by aggregation of the end-blocks, but the PFPO blocks tended to adopt disk-like or even sheet-like structures. This is attributed to the extremely high interfacial tension of PFPO with water and is consistent with the "super-strong" segregation regime behavior. The heterotelechelic PB-b-PEO- b-PFPO terpolymers adopted a quite different structure, namely an intricate bicontinuous open-cell foam, with cells on the order of 500 nm in size and cell walls composed of PFPO disks embedded in PB sheets. These various network structures illustrate the potential of using end-block chemistry to manipulate both the morphology and the physical properties of polymer gels. Dilute aqueous solutions containing 1 wt% cetyltrimethylammonium tosylate, a surfactant well recognized to form wormlike

  3. Free radical (co)polymerization of methyl methacrylate and styrene in room temperature ionic liquids (United States)

    Zhang, Hongwei

    Conventional free radical polymerizations were carried out in a variety of room temperature ionic liquids (RTILs). Generally, methyl methacrylate (MMA) and styrene (St) were used as typical monomers to compare the polymerization behavior both in RTILs and in common volatile organic compound solvents (VOCs). In most cases, it was observed that both yields and molecular weights are enhanced in the RTIL. While we believe the "diffusion-controlled termination" mechanism makes the termination of the radical propagating chains difficult due to the highly viscous nature of RTIL, other researchers have suggested that the rapid polymerization rates are due to the high polarity of these reaction media. By employing more than a dozen RTILs with a wide range of anions and cations, we attempted to correlate the viscosity and polarity of the RTILs with the molecular weights and polymerization rates. This correlation was not successful, suggesting that other parameters may also play a role in affecting the polymerization behavior. Other kinds of polymerizations have also been attempted including nitroxide-mediated living radical polymerizations of St and MMA in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), and redox initiation system initiated polymerization of MMA through redox pair formed by cation of trihexyl-tetradecyl-phosphonium bis(2,4,4-trimethylpentyl) phosphinate ([H3TDP] [(PM3) 2P]) and BPO. The formation of PSt-b-PMMA by sequential monomer addition through the standard free radical polymerization mechanism, using BPO as initiator, can be realized in [BMIM]PF6 due to the insolubility of polymerized first block---PSt in [BMIM]PF6. The macroradicals wrapped inside the chain coils have prolonged lifetimes because of the diminished termination, which allow some of these radicals to initiate polymerization of MMA at room temperature to form diblock copolymer. Solvents effects on reactivity ratios for free radical statistical copolymerization have been

  4. Poloxamer-Decorated Polymer Nanoparticles for Lung Surfactant Compatibility

    DEFF Research Database (Denmark)

    Beck-Broichsitter, Moritz; Bohr, Adam; Ruge, Christian A


    (styrene) and poly(lactide) nanoparticle-induced lung surfactant inhibition could be related to the type and content of the applied poloxamer. Escalations of the adsorbed coating layer thickness (>3 nm) as well as concentration (brush- rather than mushroom-like conformation of poly(ethylene glycol), chain......Lung-delivered polymer nanoparticles provoked dysfunction of the essential lung surfactant system. A steric shielding of the nanoparticle surface with poloxamers could minimize the unwanted interference of polymer nanoparticles with the biophysical function of lung surfactant. The extent of poly......-associated proteins. Poloxamer-modified polymer nanoparticles represent a promising nanomedicine platform intended for respiratory delivery revealing negligible effects on the biophysical functionality of the lining layer present in the deep lungs....

  5. Composite polymer nanoarchitectures from a one-pot hydrothermal route. (United States)

    Yu, Shirong; Chang, Ying; Yuan, Conghui; Wang, Shuang; Mao, Jie; Chen, Guorong; Luo, Weiang; Xu, Yiting; Dai, Lizong


    Exploitation of facile and versatile synthetic approaches to polymeric nanoarchitectures is of great interest in polymer science and engineering. Herein, we show that a simple hydrothermal route using double-solvents as reaction media has the ability to generate polymer nanospheres with tunable morphologies and components. In this one-pot approach, condensation polymerization of a resol precursor and radical polymerization of styrene are allowed to occur simultaneously under hydrothermal treatment. The synergistic self-organization of phenol-formaldehyde crosslinked networks and polystyrene chains leads to the formation of well-defined hollow nanospheres with adjustable shell thickness or even Janus particles comprising a solid hemisphere and a hollow hemisphere. Furthermore, control over the composition of the hollow polymer nanospheres can be easily achieved by introducing a third monomer into the hydrothermal system.

  6. Creep Behavior of ABS Polymer in Temperature-Humidity Conditions (United States)

    An, Teagen; Selvaraj, Ramya; Hong, Seokmoo; Kim, Naksoo


    Acrylonitrile-Butadiene-Styrene (ABS), also known as a thermoplastic polymer, is extensively utilized for manufacturing home appliances products as it possess impressive mechanical properties, such as, resistance and toughness. However, the aforementioned properties are affected by operating temperature and atmosphere humidity due to the viscoelasticity property of an ABS polymer material. Moreover, the prediction of optimum working conditions are the little challenging task as it influences the final properties of product. This present study aims to develop the finite element (FE) models for predicting the creep behavior of an ABS polymeric material. In addition, the material constants, which represent the creep properties of an ABS polymer material, were predicted with the help of an interpolation function. Furthermore, a comparative study has been made with experiment and simulation results to verify the accuracy of developed FE model. The results showed that the predicted value from FE model could agree well with experimental data as well it can replicate the actual creep behavior flawlessly.

  7. α,β-Unsubstituted meso-Positioning Thienyl BODIPY: A Promising Electron Deficient Building Block for the Development of Near Infrared (NIR) p-type Donor-Acceptor (D-A) Conjugated Polymers

    KAUST Repository

    Squeo, Benedetta


    It is demonstrated that α,β-unsubstituted meso-positioning thienyl BODIPY is an electron deficient unit that leads to the development of ultra low optical band gap (Egopt < 1 eV) π-conjugated D-A quarterthiophene polymers. Furthermore, it is revealed that the optoelectronic, electrochemical and charge transporting properties of the resulting α,β-unsubstituted meso-positioning thienyl BODIPY quaterthiophene-based polymers are alkyl side chain positioning dependent. Tail-to-tail (TT) positioning of the alkyl side chains at the two central thiophenes of the quaterthiophene segment results to lower Egopt, higher energy levels and increased hole mobility as compared to head-to-head (HH) positioning. Finally, even though the synthesized polymers exhibit high electron affinity, higher even to that of the fullerene derivative [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), they present only p-type behaviour in field effect transistors (FETs) independent to the alkyl side chain positioning.

  8. Polymer Electrolytes (United States)

    Hallinan, Daniel T.; Balsara, Nitash P.


    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  9. Star Polymers. (United States)

    Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G


    Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

  10. Polymer Chemistry (United States)

    Williams, Martha; Roberson, Luke; Caraccio, Anne


    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  11. Metallization of Various Polymers by Cold Spray (United States)

    Che, Hanqing; Chu, Xin; Vo, Phuong; Yue, Stephen


    Previous results have shown that metallic coatings can be successfully cold sprayed onto polymeric substrates. This paper studies the cold sprayability of various metal powders on different polymeric substrates. Five different substrates were used, including carbon fiber reinforced polymer (CFRP), acrylonitrile butadiene styrene (ABS), polyether ether ketone (PEEK), polyethylenimine (PEI); mild steel was also used as a benchmark substrate. The CFRP used in this work has a thermosetting matrix, and the ABS, PEEK and PEI are all thermoplastic polymers, with different glass transition temperatures as well as a number of distinct mechanical properties. Three metal powders, tin, copper and iron, were cold sprayed with both a low-pressure system and a high-pressure system at various conditions. In general, cold spray on the thermoplastic polymers rendered more positive results than the thermosetting polymers, due to the local thermal softening mechanism in the thermoplastics. Thick copper coatings were successfully deposited on PEEK and PEI. Based on the results, a method is proposed to determine the feasibility and deposition window of cold spraying specific metal powder/polymeric substrate combinations.

  12. Raman Spectroscopy of 3-D Printed Polymers (United States)

    Espinoza, Vanessa; Wood, Erin; Hight Walker, Angela; Seppala, Jonathan; Kotula, Anthony

    Additive manufacturing (AM) techniques, such as 3-D printing are becoming an innovative and efficient way to produce highly customized parts for applications ranging from automotive to biomedical. Polymer-based AM parts can be produced from a myriad of materials and processing conditions to enable application-specific products. However, bringing 3-D printing from prototype to production relies on understanding the effect of processing conditions on the final product. Raman spectroscopy is a powerful and non-destructive characterization technique that can assist in determining the chemical homogeneity and physical alignment of polymer chains in 3-D printed materials. Two polymers commonly used in 3-D printing, acrylonitrile butadiene styrene (ABS) and polycarbonate (PC), were investigated using 1- and 2-D hyperspectral Raman imaging. In the case of ABS, a complex thermoplastic, the homogeneity of the material through the weld zone was investigated by comparing Raman peaks from each of the three components. In order to investigate the effect of processing conditions on polymer chain alignment, polarized Raman spectroscopy was used. In particular, the print speed or shear rate and effect of strain on PC filaments was investigated with perpendicular and parallel polarizations. National Institute of Standards and Technology Gaithersburg, MD ; Society of Physics Students.

  13. Swelling of organoclays in styrene. Effect on flammability in polystyrene nanocomposites

    Directory of Open Access Journals (Sweden)


    Full Text Available In this work the effect of the compatibility between organoclays and styrene on the flammability of polystyrene/clay nanocomposites obtained through in situ incorporation was investigated. The reactions were carried out by bulk polymerization. The compatibility between organoclays and styrene was inferred from swelling of the organoclay in styrene. The nanocomposites were characterized by X-ray diffraction and Transmission Electron Microscopy. The heat release rate was obtained by Cone Calorimeter and the nanocomposites were tested by UL94 horizontal burn test. Results showed that intercalated and partially exfoliated polystyrene/clay nanocomposites were obtained depending on the swelling behavior of the organoclay in styrene. The nanocomposites submitted to UL94 burning test presented a burning rate faster than the virgin polystyrene (PS, however an increase of the decomposition temperature and an accentuated decrease on the peak of heat release of the nanocomposites were also observed compared to virgin PS. These results indicate that PS/clay nanocomposites, either intercalated or partially exfoliated, reduced the flammability approximately by the same extent, although reduced the ignition resistance of the PS.

  14. 0177 Exposure to styrene and the risk of cancer

    DEFF Research Database (Denmark)

    Christensen, Mette Skovgaard; Hansen, J; Ramlau-Hansen, Cecilia


    following occupational styrene exposure. METHOD: The cohort consists of 74 902 workers (84% men) in the Danish reinforced plastics industry, originating from 481 companies ever producing reinforced plastics in Denmark 1964-2009. We identified all workers in the National Supplementary Pension Fund Registry...

  15. Cyclodimerization of Stilbenes and Styrenes Catalyzed by Heteropolyacid Supported on Silica

    Directory of Open Access Journals (Sweden)

    B. Lantaño


    Full Text Available Several stilbenes and styrenes have been treated with heteropolyacid] (HPA supported over silice. The compounds obtained were characterized by 1H and 13C- NMR and the yields were compared with those obtained using H2SO4 (c and ethyl poliphosphate] (PPE.


    The report gives results of an evaluation of several conventional and novel emission control technologies that have been used or could be used to treat styrene emissions from open molding processes in fiberglass-reinforced plastics/composites (FRP/C) and fiberglass boat building ...

  17. Development of bioconjugated dye-doped poly(styrene-co-maleimide) nanoparticles as a new bioprobe

    CSIR Research Space (South Africa)

    Swanepoel, A


    Full Text Available -1 Journal of Materials Chemistry B Development of bioconjugated dye-doped poly(styrene-co- maleimide) nanoparticles as a new bioprobe A. Swanepoel, I. du Preez, T. Mahlangu, A. Chetty and B. Klumperman Abstract Fluorescent dye-doped poly...

  18. 40 CFR 721.3700 - Fatty acid, ester with styrenated phenol, ethylene oxide adduct. (United States)


    ... phenol, ethylene oxide adduct. 721.3700 Section 721.3700 Protection of Environment ENVIRONMENTAL..., ethylene oxide adduct. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acid, ester with styrenated phenol, ethylene oxide...

  19. Expanding Upon Styrene Biosynthesis to Engineer a Novel Route to 2-Phenylethanol. (United States)

    Machas, Michael S; McKenna, Rebekah; Nielsen, David R


    2-Phenylethanol (2PE) is a key molecule used in the fragrance and food industries, as well as a potential biofuel. In contrast to its extraction from plant biomass and/or more common chemical synthesis, microbial 2PE production has been demonstrated via both native and heterologous expression of the yeast Ehrlich pathway. Here, a novel alternative to this established pathway is systematically engineered in Escherichia coli and evaluated as a more robust and efficient route. This novel pathway is constructed via the modular extension of a previously engineered styrene biosynthesis pathway, proceeding from endogenous l-phenylalanine in five steps and involving four heterologous enzymes. This "styrene-derived" pathway boasts nearly a 10-fold greater thermodynamic driving force than the Ehrlich pathway, and enables reduced accumulation of acetate byproduct. When directly compared using a host strain engineered for l-phenylalanine over-production, preservation of phosphoenolpyruvate, and reduced formation of byproduct 2-phenylacetic acid, final 2PE titers via the styrene-derived and Ehrlich pathways reached 1817 and 1164 mg L-1 , respectively, at yields of 60.6 and 38.8 mg g-1 . Following optimization of induction timing and initial glucose loading, 2PE titers by the styrene-derived pathway approached 2 g L-1 - nearly a two-fold twofold increase over prior reports for 2PE production by E. coli employing the Ehrlich pathway. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Breath and blood levels of benzene, toluene, cumene and styrene in non-occupational exposure. (United States)

    Brugnone, F; Perbellini, L; Faccini, G B; Pasini, F; Maranelli, G; Romeo, L; Gobbi, M; Zedde, A


    Benzene, toluene, cumene and styrene were measured in the breath and blood of two groups of individuals. The first group included individuals belonging to a hospital staff, the second group included chemical workers who were not exposed to the abovementioned chemicals. The chemical workers were examined in plant infirmaries on the morning before the start of the workshift, and the hospital staff in the hospital infirmaries. One environmental air sample was taken in the infirmaries for each individual at the moment of the biological samplings. The environmental concentrations of benzene and styrene were significantly higher in the infirmaries of the chemical plant than in the infirmaries of the hospital. On the other hand, the environmental concentrations of toluene and cumene were not significantly different in the plant infirmaries and in the hospital infirmaries. In the hospital staff the alveolar concentrations of benzene, toluene and styrene were significantly lower than those in the chemical workers. In the hospital staff the blood concentrations of benzene, toluene and styrene were not significantly different from those in the chemical workers. Only the blood cumene concentration was significantly higher in the chemical workers. In hospital staff, smokers showed alveolar and blood concentrations of benzene and toluene that were significantly higher than those measured in the non smoker hospital staff. With reference to chemical workers, only alveolar benzene concentration was significantly higher in smokers than in non smokers.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. Embryotoxic and teratogenic effects of styrene derivatives on sea urchin development. (United States)

    Pagano, G; Esposito, A; Giordano, G G; Hagström, B E


    The effects of styrene and some of its derivatives on the fertilization and differentiation of sea urchins was investigated. When one of the gametes was pretreated for a few minutes, it was ascertained that the test substances act on the haploid nucleus, producing specific changes in the differentiation of the embryo. By this test system directly acting, weak mutagens may be detected.

  2. Global styrene oligomers monitoring as new chemical contamination from polystyrene plastic marine pollution. (United States)

    Kwon, Bum Gun; Koizumi, Koshiro; Chung, Seon-Yong; Kodera, Yoichi; Kim, Jong-Oh; Saido, Katsuhiko


    Polystyrene (PS) plastic marine pollution is an environmental concern. However, a reliable and objective assessment of the scope of this problem, which can lead to persistent organic contaminants, has yet to be performed. Here, we show that anthropogenic styrene oligomers (SOs), a possible indicator of PS pollution in the ocean, are found globally at concentrations that are higher than those expected based on the stability of PS. SOs appear to persist to varying degrees in the seawater and sand samples collected from beaches around the world. The most persistent forms are styrene monomer, styrene dimer, and styrene trimer. Sand samples from beaches, which are commonly recreation sites, are particularly polluted with these high SOs concentrations. This finding is of interest from both scientific and public perspectives because SOs may pose potential long-term risks to the environment in combination with other endocrine disrupting chemicals. From SOs monitoring results, this study proposes a flow diagram for SOs leaching from PS cycle. Using this flow diagram, we conclude that SOs are global contaminants in sandy beaches around the world due to their broad spatial distribution. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Prognosis and determination of the threshold of chronic effect of carbon disulfide and styrene

    Energy Technology Data Exchange (ETDEWEB)

    Popov, T.; Zaprianov, Z.; Benchev, I.; Spasovski, M.


    Two series of studies were carried out: I--in workers exposed to four different mean annual CS/sub 2/ concentrations(6 mg/m3m3; 12 mg/m3; 51 mg/m3 and 247 mg/m3 and II series) in workers exposed to three styrene concentrations-(-I mg/m3; 40 mg/m3 and 400 mg/m3). The results obtained in series I show the role of the primary toxic effect (inhibition of oxidases with mixed function) and of the adaptation reactions to it with a view to accurate specifying the threshold of chronic CS/sub 2/ effect. The mathematical expression of the correlation between styrene concentration in air and blood, of phenyl-glyoxylic and mandelic acid in the urine of the exposed subjects enables the prognosis that the threshold of the noxious styrene effect is within the range of 150 mg/m3 to 250 mg/m3. A reduction on CS/sub 2/ MAC is proposed-(-from 10 mg/m3 to I mg/m3) and the correction of styrene MAC-(-from 5 mg/m3 to 30-50 mg/m3).

  4. Particle reinforced composites from acrylamide modified blend of styrene-butadiene and natural rubber (United States)

    Blends of styrene-butadiene rubber and natural rubber that provide balanced properties were modified with acrylamide and reinforced with soy protein particles. The rubber composites show improved mechanical properties. Both modified rubber and composites showed a faster curing rate. The crosslinking...

  5. Ultrasound guided supraclavicular block.

    LENUS (Irish Health Repository)

    Hanumanthaiah, Deepak


    Ultrasound guided regional anaesthesia is becoming increasingly popular. The supraclavicular block has been transformed by ultrasound guidance into a potentially safe superficial block. We reviewed the techniques of performing supraclavicular block with special focus on ultrasound guidance.

  6. Incorporation and release of cloxacillin sodium in micelles of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide). (United States)

    Khanal, Anil; Nakashima, Kenichi


    A novel drug carrier system was constructed from anionic drug cloxacillin sodium (CLX) and micelle of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) by incorporating the former into the micelle of the latter. The incorporation of CLX into the micelle of PS-PVP-PEO was confirmed by zeta-potential measurements, dynamic light scattering (DLS), and fluorescence spectroscopy. In the absence of the anionic drug, CLX, the zeta-potential of neat PS-PVP-PEO micelle was +13 mV under aqueous acidic condition due to the presence of positive charges in the PVP unit. The addition of CLX into the micelle of PS-PVP-PEO decreased the zeta-potential of the micelle smoothly and finally led to a minimum zeta-potential around 0 mV. This fact shows that the added CLX is effectively incorporated into the PS-PVP-PEO micelle by electrostatic attraction. In concomitant with the decrease in zeta-potential, a decrease in hydrodynamic diameter from 94 to 69 nm was observed on addition of CLX to the PS-PVP-PEO micellar solution. This fact also indicates the incorporation of CLX into the PS-PVP-PEO micelles because the binding of CLX to the PVP block of the micelles induces a conformational change from an extended to a shrunken form due to the cancellation of the repulsive force in the PVP blocks by CLX. Fluorescence quenching of pyrene by CLX gave additional evidence for the effective bindings of CLX to the PS-PVP-PEO micelles. Further, release of CLX from the nanoaggregates of CLX/PS-PVP-PEO was investigated in vitro. It was found that the release kinetics of the CLX is conformed to a model based on the consecutive chemical kinetics.

  7. A novel notch filter based on block copolymer photonic crystal (United States)

    Hara, Shigeo; Yamanaka, Takahiko; Hirohata, Toru; Niigaki, Minoru


    We demonstrate filtering characteristics of a polymer notch filter (PNF) with highly-ordered microphase-separated structure of block copolymers (BCPs). This PNF is characterized by an Optical Density > 5 blocking at the center wavelength and narrow blocking full bandwidth of 8 nm. Moreover, the wavelength is easily tuned by blending two BCPs with different molecular-weight. A low frequency Raman shift of 200 cm-1 are, in fact, detected with a sufficient resolution by using this filter in Raman spectroscopy.

  8. Block copolymer self-assembly and co-assembly : shape function and application

    NARCIS (Netherlands)

    Li, F.


    Amphiphilic block copolymers can, in selective solvents such as water, assemble into various shapes and architectures. Among those, polymer vesicles, polymer micelles and polymer fibers are very popular structures in current nanotechnology. These objects each have their own particular properties and

  9. Star block-copolymers: Enzyme-inspired catalysts for oxidation of alcohols in water

    KAUST Repository

    Mugemana, Clement


    A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. This journal is © the Partner Organisations 2014.

  10. 2010 POLYMER PHYSICS - JUNE 27 - JULY 2, 2010

    Energy Technology Data Exchange (ETDEWEB)

    Karen Winey


    The 2010 Gordon Research Conference on Polymer Physics will provide outstanding lectures and discussions in this critical field that impacts every industrial sector from electronics to transportation to medicine to textiles to energy generation and storage. Fundamental topics range from mechanical properties of soft gels to new understanding in polymer crystallization to energy conversion and transmission to simulating polymer dynamics at the nanoscale. This international conference will feature 22 invited lectures, wherein the opening 10 minutes are specifically designed for a general polymer physics audience. In addition, poster sessions and informal activities provide ample opportunity to discuss the latest advances in polymer physics. The technical content of the meeting will include new twists on traditional polymer physics topics, recent advances in previously underrepresented topics, and emerging technologies enabled by polymer physics. Here is a partially listing of targeted topics: (1) electrically-active and light-responsive polymers and polymer-based materials used in energy conversion and storage; (2) polymers with hierarchical structures including supramolecular assemblies, ion-containing polymers, and self-assembled block polymers; (3) mechanical and rheological properties of soft materials, such as hydrogels, and of heterogeneous materials, particularly microphase separated polymers and polymer nanocomposites; and (4) crystallization of polymers in dilute solutions, polymer melts, and miscible polymer blends.

  11. Sorption of 2-Chlorophenol from aqueous solutions by functionalized cross-linked polymers

    Directory of Open Access Journals (Sweden)

    Rodrigo Martins Fráguas


    Full Text Available This manuscript describes the synthesis of three polymers based on styrene (STY, divinylbenzene (DVB and two different vinyl monomers: methyl methacrylate (MMA and acrylonitrile (AN. The STY-DVB, STY-DVB-MMA and STY-DVB-AN polymers were synthesized employing the aqueous suspension technique. Reaction yields were 73%, 81% and 75%, respectively. They were morphological and chemically characterized using different techniques. The extraction capacity of the polymers was evaluated using 2-chlorophenol. The polymer extraction capacities were evaluated varying contact time the (1 h, 3 h and 5 h, temperature (30 °C, 35 °C and 40 °C, and pH (3, 5.6 and 8. The STY-DVB-AN polymer was the most efficient; it removed around 95% of the analyte using a contact time 50 h.

  12. Branched polymers on branched polymers


    Durhuus, Bergfinnur; Jonsson, Thordur


    We study an ensemble of branched polymers which are embedded on other branched polymers. This is a toy model which allows us to study explicitly the reaction of a statistical system on an underlying geometrical structure, a problem of interest in the study of the interaction of matter and quantized gravity. We find a phase transition at which the embedded polymers begin to cover the basis polymers. At the phase transition point the susceptibility exponent $\\gamma$ takes the value 3/4 and the ...

  13. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry


    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  14. Simulation of the styrene production process via catalytic dehydrogenation of ethylbenzene using CHEMCAD® process simulator

    Directory of Open Access Journals (Sweden)

    Amaury Pérez Sánchez


    Full Text Available Background: Process simulation has been extensively used in recent years to design, evaluate or optimize processes, systems and specific operations of the chemical industry and its related disciplines. Currently, CHEMCAD® constitute one of the most used process simulators because of the great number of chemical and petrochemical processes that can be simulated. Method: The simulation of the production process of styrene via catalytic dehydrogenation of ethyl-benzene is carried out by using the process simulator CHEMCAD® version 5.2.0, in order to determine the composition and mass flow-rate of each process involved in the production, as well as the main operating parameters of the equipment used. Two sensitivity studies were carried out: firstly, the influence of the temperature and pressure values applied at the LLV Separator on the amounts of ethyl-benzene and styrene to be obtained by the intermediate and top currents of this equipment; secondly, the influence of the operating pressure of the Distillation Column No. 1 (benzene-toluene column on the quantity of ethyl-benzene and styrene obtained at the bottom stream. The simulating software MATLAB® version 7.8.0 was used to process the results obtained. Results: Around 9234.436 kg/h of styrene is obtained in the last distillation column with 99.6% purity. Additionally, it was found that the water is the main impurity found on this stream, which represents 0.35% of the weight. Conclusions: The LLV Separator must operate at a low temperature (5 – 10 ºC and at a relatively high pressure (10 bar, whereas the Distillation Column No. 1 must work at a pressure near atmospheric (1.0 bar, or preferably under vacuum conditions in order to obtain the highest yields of styrene and ethyl-benzene.

  15. Transparent nanostructured photochromic UV-blocking soft contact lenses. (United States)

    Pek, Y Shona; Wu, Hong; Chow, Edwin Py; Ying, Jackie Y


    We aim to develop transparent UV-blocking photochromic soft contact lenses via polymerization of a bicontinuous nanoemulsion. Transparent nanostructured polymers were prepared by incorporating a polymerizable surfactant and thermal initiator together with water, monomers, UV blockers and photochromic dyes. The polymers were characterized using oxygen permeometer, tensile tester, electron microscope, UV spectrophotometer, corneal cell culture and testing in rabbits. The polymers have good oxygen permeability, water content, stiffness, strength and UV-blocking ability comparable to commercial UV-blocking soft contact lenses. Their response to UV light is comparable to photochromic spectacle lenses, particularly in reverse transition from colored to colorless state. They are nontoxic and nonleaching. Our photochromic UV-blocking contact lenses provide a novel alternative to photochromic spectacles.

  16. Conducting Polymers

    Indian Academy of Sciences (India)

    potential of the monomer would be less than that of the dimer, which would in turn be less than that of the polymer. Hence, the polymer generated by this oxidative .... glucose and galactose biosensors based on a silicon chip employing polypyrrole have in fact been developed by several companies. These types of sensors ...

  17. Conducting Polymers

    Indian Academy of Sciences (India)

    polymer backbone), exhibit semiconducting behavior. The discovery of dopingl led to a further dramatic increase in the conductivity of such conjugated polymers to values as ..... CERF's Comments on Modem Science. • If it's incomprehensible, it's mathematics. • If it doesn't make sense, it's either economics or psychology.

  18. Polymers & People (United States)

    Lentz, Linda; Robinson, Thomas; Martin, Elizabeth; Miller, Mary; Ashburn, Norma


    Each Tuesday during the fall of 2002, teams of high school students from three South Carolina counties conducted a four-hour polymer institute for their peers. In less than two months, over 300 students visited the Charleston County Public Library in Charleston, South Carolina, to explore DNA, nylon, rubber, gluep, and other polymers. Teams of…

  19. Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Zhu, Kaizheng; Nyström, Bo


    By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA...... block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can...... show simultaneous microphase (between Linear and AmphComb blocks) and nanophase (within the AmphComb blocks) separations. This leads to the formation of various structure-in-structure two-scale hierarchical self-assemblies, including S-in-SLL, S-in-SBCC, S-in-C, S-in-L and C-in-L, where S, SLL, SBCC, C...

  20. Solid-state nuclear magnetic resonance studies of vinyl polymer/silica colloidal nanocomposite particles. (United States)

    Lee, Daniel; Balmer, Jennifer A; Schmid, Andreas; Tonnar, Jeff; Armes, Steven P; Titman, Jeremy J


    Solid-state nuclear magnetic resonance (NMR) has been used to characterize the interface between the organic and inorganic components of "core-shell" colloidal nanocomposite particles synthesized by in situ aqueous (co)polymerization of styrene and/or n-butyl acrylate in the presence of a glycerol-functionalized silica sol. Polymer protons are in close proximity (nanocomposites studied, indicating that either styrene or n-butyl side groups extend between the glycerol-functional silane molecules toward the surface of the silica particles. For the poly(styrene-co-n-butyl acrylate)/silica nanocomposite n-butyl acrylate residues are located closer to the surface of the silica particle than styrene residues, suggesting a specific interaction between the former and the glycerol-functionalized silica surface. The most likely explanation is a hydrogen bond between the ester carbonyl and the glycerol groups, although this cannot be observed directly. For the Bindzil CC40 glycerol-functionalized silica sol the relative intensities of (29)Si NMR lines corresponding to T and Q(3) environments imply that there are approximately twice as many unreacted silanol groups on the silica surface as attached silane molecules.