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1.
Polypyrrole-coated poly(vinyl chloride) powder particles (PPy-PVC) were prepared by the in-situ chemical polymerization of pyrrole in aqueous solutions in the presence of PVC powder particles using the method of Ouyang and Chan [Polymer 39 (1998) 1857] and characterized by inverse gas chromatography (IGC). By employing n-alkane, 1-heptene, chloroform and tetrahydrofuran molecular probes, the dispersive and acid–base components of the surface energy of the composite materials were estimated at infinite dilution. The values of the dispersive contribution to the surface energy (γSd), at 50 °C, range from 30.3 to 43.5 mJ/m2 for the composites, which is much lower than the value of 83.2 mJ/m2 obtained for para-toluene sulfonate-doped polypyrrole (PPyTS) bulk powder. This indicates that the injected molecules probe both polypyrrole and the underlying PVC, thus indicating that the conducting polymer is rather patchy at the surface of the insulating polymer substrate. This conclusion supports the previous results obtained by X-ray photoelectron spectroscopy (XPS) [19], indicating that both the coating PPyTS and the substrate PVC are detected by their elemental markers nitrogen and sulfur, and chlorine, respectively.  相似文献   

2.
Aqueous chemical oxidative dispersion polymerizations of pyrrole using PdCl2 oxidant were conducted using water-soluble polymeric colloidal stabilizers in order to synthesize polypyrrole–palladium (PPy–Pd) nanocomposite particles in one step. PPy–Pd nanocomposite particles with number average diameters of approximately 30 nm were successfully obtained as colloidally stable aqueous dispersions, which were stable at least for 7 months, using poly(4-lithium styrene sulfonic acid) colloidal stabilizer. The resulting nanocomposite particles were extensively characterized with respect to particle size, size distribution, colloidal stability, nanomorphology, surface/bulk chemical compositions, and conductivity. X-ray photoelectron spectroscopy indicated the existence of poly(styrene sulfonic acid) colloidal stabilizer on the surface of the nanocomposite particles. Transmission electron microscopy studies confirmed that nanometer-sized Pd nanoparticles were distributed in the PPy matrix.  相似文献   

3.
Polypyrrole was chemically synthesised by using, for the first time, Birchwood xylan as additive, and ammonium peroxydisulfate (APS) as oxidant. The impact of additive concentration, polymerisation time and reagents concentration on PPy conductivity was studied. It was shown that, once fixed the pyrrole (Py)/APS and Py/xylan optimal ratios, the best conductivities (26 S/cm) were obtained for short polymerisation times (30 min) and increased reactants concentration. Morphological analysis of PPy particles, Py depletion kinetics and oxido-reduction potential measurements of the solutions provided interpretation elements on the impact of the polymerisation time on PPy pellet conductivity. Furthermore, optimised PPy particles obtained with xylan (PPyx) were mixed with nanofibrillated cellulose (NFC) in order to obtain freestanding films. Their electrical and handling performances were evaluated at increasing PPy weight fraction in the samples. The conductivity mechanism of the most conductive sample (in comparison with a low performing sample) was investigated by measuring the conductivity as a function of temperature (4–350 K) and two transport regimes were identified. Selected formulations were finally used to produce conducting PPy/NFC coatings on non-absorbent (glass) and absorbent (copy paper) substrates. The impact of NFC in the percolation of PPy particles, then in the coating conductivity, was investigated.  相似文献   

4.
Polypyrrole/iron oxide (PPy/γ-Fe2O3) nanocomposites were synthesized by in situ oxidative polymerization of pyrrole in the presence of surface modified γ-Fe2O3 in supercritical carbon dioxide (scCO2). The structural properties of nanocomposite particles thus obtained were characterized by FT-IR, thermal analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It was found that ca. 50 nm γ-Fe2O3 nanoparticles were well dispersed in PPy powder in TEM pictures. X-ray photoelectron spectroscopy (XPS) analysis also support that all γ-Fe2O3 nanoparticles are encapsulated by PPy. Magnetic property of the nanocomposites was measured by SQUID, which indicated that the nanocomposites are superparamagnetic. The effects of different loadings of γ-Fe2O3 on the polymerization were also investigated.  相似文献   

5.
This paper describes a method for polypyrrole (PPy) coating of metallic Cu nanoparticles in aqueous solution in atmosphere. Colloid solution of Cu nanoparticles was prepared by reducing Cu ions with the use of hydrazine in an aqueous solution dissolving citric acid and cetyltrimethylammonium bromide as stabilizers. The PPy coating was performed by polymerizing pyrrole with the use of hydrogen peroxide as an initiator in an aqueous colloid solution of the Cu nanoparticles. Ultraviolet–visible extinction measurements, transmission electron microscopy observation, and X-ray diffraction measurements revealed that the metallic Cu nanoparticles with a size of 27.6 ± 11.1 nm were coated with PPy. The obtained PPy-coated Cu particles were chemically stable even in atmosphere.  相似文献   

6.
Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl3 as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen 1H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

7.
Electrically conductive polypyrrole (PPy)/poly(methyl methacrylate) (PMMA) core-shell nanoparticles were synthesized by two-step microemulsion polymerization. PPy core particles were prepared in a four-component microemulsion system, which was formed with surfactant cetyltrimethyl ammonium bromide (CTAB), cosurfactant n-pentanol, water, and pyrrole. Ferric chloride and iodine was added as the oxidant and the dopant, respectively. Then the PPy nanoparticles were coated with PMMA to prepare PPy/PMMA core-shell nanoparticles. The morphology of PPy/PMMA core-shell nanoparticles was characterized with transmission electron microscopy (TEM). Fourier transform infrared (FTIR) spectroscopy was used to characterize the structure of the samples. The electrical conductivities of samples were studied by a Hall effect testing instrument. Despite being coated with a layer of insulation, the conductivity of the composite PPy/PMMA core-shell nanoparticles could still reached to 7.856 × 10?1 S/cm.  相似文献   

8.
Uniform Fe3O4 nanospheres with a diameter of 100 nm were rapidly prepared using a microwave solvothermal method. Then Fe304/polypyrrole (PPy) composite nanospheres with well-defined core/shell structures were obtained through chemical oxidative polymerization of pyrrole in the presence of Fe3O4; the average thickness of the coating shell was about 25 nm. Furthermore, by means of electrostatic interactions, plentiful gold nanoparticles with a diameter of 15 nm were assembled on the surface of Fe3O4/PPy to get Fe3O4/PPy/Au core/shell/shell structure. The morphology, structure, and composition of the products were characterized by transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), X-ray powder diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. The resultant nanocomposites not only have the magnetism of Fe3O4 nanoparticles that make the nanocomposites easily controlled by an external magnetic field but also have the good conductivity and excellent electrochemical and catalytic properties of PPy and Au nanoparticles. Furthermore, the nanocomposites showed excellent electrocatalytic activities to biospecies such as ascorbic acid (AA).  相似文献   

9.
In order to exploit the applications of polypyrrole (PPy) derivatives in biosensors and bioelectronics, the different immobilization mechanisms of biomolecules onto differently functionalized conducting PPy films are investigated. Pyrrole and pyrrole derivatives with carboxyl and amino groups were copolymerized with ω‐(N‐pyrrolyl)‐octylthiol self‐assembled on Au surface by the method of the chemical polymerization to form a layer of the copolymer film, i.e., poly[pyrrole‐co‐(N‐pyrrolyl)‐caproic acid] (poly(Py‐co‐PyCA)) and poly[pyrrole‐co‐(N‐pyrrolyl)‐hexylamine] (poly(Py‐co‐PyHA)), in which the carboxyl groups in poly(Py‐co‐PyCA) were activated to the ester groups. Based on the structure characteristics, the immobilization/hybridization of DNA molecules on PPy, poly(Py‐co‐PyCA) and poly(Py‐co‐PyHA) were surveyed by cyclic voltammograms measurements. For differently functionalized copolymers, the immobilization mechanisms of DNA are various. Besides the electrochemical properties of the composite electrodes of PPy and its copolymers being detected before and after bovine serum albumin (BSA) adsorption, the kinetic process of protein binding was determined by surface plasmon resonance of spectroscopy. Since few BSA molecules could anchor onto the PPy and its copolymers surfaces, it suggests this kind of conducting polymers can be applied as the protein‐resistant material.  相似文献   

10.
All-solid-state ion-selective electrodes with plastic membrane (poly(vinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS), methyltri-n-tetradecylammonium chloride (MTTACl)), a conducting poly(pyrrole) (PPy) film doped either with chloride ions (PPyCl) or hexacyanoferrate(II) ions (PPyFeCN), and glassy carbon (GC) or screen-printed graphite layer (S-PG) as an inner electric contact were investigated. All the electrodes show close to Nernstian response, but their lifetimes vary. The at least 2-months lifetime of screen-printed electrodes is only achieved for the electrodes containing PPyFeCN (cation-exchanging film). Shorter lifetime of other screen-printed electrodes, i.e. without PPy, or with PPyCl (anion-exchanging film), was attributed to the diffusion of anionic products of the hydrolysis of organic components of the graphite paste used to prepare the electric contact. The properties of miniature, screen-printed electrodes comprising PPyFeCN solid contact, were comparable to those ion-selective electrodes with PPy solid contact (regardless the ion-exchanging characteristic of the polymer) deposited on GC electric contact.  相似文献   

11.
Poly(vinyl amine) (PVAm) was derivatised using 2-thiophenecarboxaldehyde via Michael addition to prepare a statistical copolymer stabiliser for the synthesis of primary amine-functionalised polypyrrole (PPy) particles. A minimum stabiliser concentration of around 20 % (w/v) relative to pyrrole was required for well-defined PPy particles of approximately 100–200 nm, as judged by transmission electron microscopy (TEM) and dynamic light scattering (DLS). FTIR spectroscopy confirmed that stabiliser grafting had occurred, while x-ray photoelectron spectroscopy (XPS) studies indicated a stabiliser surface coverage on the PPy particles of around 53 %. PPy particles prepared at stabiliser concentrations below 20 % (w/v) were not colloidally stable above pH 6. However, higher stabiliser concentrations (e.g., 50 % (w/v) based on pyrrole) led to a significant improvement, with colloidal stability being retained above pH 7. Long-term colloidal stability studies of PPy particles stored at pH 7.5 confirmed that the amine-based stabiliser produced more stable aqueous dispersions than the imine-based stabiliser, since the latter bond is hydrolytically unstable.  相似文献   

12.
Polypyrrole–FePO4 powder was synthesized by an oxidative polymerization of pyrrole monomer on the surface of FePO4 powder. The polymerization reaction was initiated using hydrogen peroxide in an acidified solution and catalysed with Fe3+. The samples were investigated by light microscopy (LM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). These methods confirmed the presence of polypyrrole on FePO4 particles and its homogeneous distribution in the composite material. To determine the PPy content in the PPy–FePO4 composites a thermogravimetric analysis was used. Cyclic voltammetry curves (CV) were measured and compared in a non-aqueous lithium salt solution for electrodes consisting of pellets made from pure FePO4 and FePO4/PPy. Electrochemical impedance spectroscopy (EIS) showed that coating of PPy significantly decreases the charge transfer resistance of PPy–FePO4 electrodes.  相似文献   

13.
Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.  相似文献   

14.
The synthesis of supramolecular conducting nanowires can be achieved by using DNA and pyrrole. Oxidation of pyrrole in DNA-containing solutions yields a material that contains both the cationic polypyrrole (PPy) and the anionic DNA polymers. Intimate interaction of the two polymer chains in the self-assembled nanowires is indicated by FTIR spectroscopy. AFM imaging shows individual nanowires to be continuous, approximately 5 nm high and conformationally flexible. This feature allows them to be aligned by molecular combing in a similar manner to bare DNA and provides a convenient method for fabricating a simple electrical device by stretching DNA/PPy strands across an electrode gap. Current-voltage measurements confirm that the nanowires are conducting, with values typical for a polypyrrole-based material. In contrast to polymerisation of pyrrole on a DNA template in bulk solution, attempts to form similar wires by polymerisation at surface-immobilised DNA do not give a continuous coverage; instead, a beads-on-a-string appearance is observed suggesting that immobilisation inhibits the assembly process.  相似文献   

15.
In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole (SIPPy) nanocomposite with core-shell structure. The composite was characterized by elemental analysis, X-ray diffraction, scanning/transmission electron microscopy, and electrochemical measurements. XRD and FTIR results showed that sulfur well dispersed in the core-shell structure and PPy structure was successfully obtained via in situ oxidative polymerization of pyrrole on the surface of sulfur particles. TEM observation revealed that PPy was formed and fixed to the surface of sulfur nanoparticle after polymerization, developing a well-defined core-shell structure and the thickness of PPy coating layer was in the range of 20-30 nm. In the composite, PPy worked as a conducting matrix as well as a coating agent, which confined the active materials within the electrode. Consequently, the as prepared SIPPy composite cathode exhibited good cycling and rate performances for rechargeable lithium/sulfur batteries. The resulting cell containing SIPPy composite cathode yields a discharge capacity of 1039 mAh·g^-1 at the initial cycle and retains 59% of this value over 50 cycles at 0.1 C rate. At 1 C rate, the SIPPy composite showed good cycle stability, and the discharge capacity was 475 mAh·g^-1 after 50 cycles.  相似文献   

16.
Electrically conductive films were obtained by solid phase photopolymerization of pyrrole (Py) into a poly(vinylchloride) (PVC) matrix. We attempted to characterize the structure, electrochemical and thermal properties, and morphology of the resulting polypyrrole/PVC blend. The blend obtained has low conductivity and rather poor electroactivity due to the loss of conjugation length of polypyrrole (PPy) provoked by halogenation. Micrographs of cryofracture surface suggested two distinct phases, and thermogravimetric analysis revealed a low thermal stability of the blend. On the basis of our experimental results, we propose a reaction mechanism that explains the PPy formation in solid phase induced by UV light.  相似文献   

17.

New polypyrrole (PPy)-derived polymer/ZrO2 nanocomposite materials are prepared by single-step oxidative polymerization of pyrrole (Py) and/or N-methylpyrrole (mPy) in the presence of HCl-functionalized ZrO2 nanoparticles and ammonium persulfate. The physicochemical features of the PPy–ZrO2, poly(Py-co-mPy)–ZrO2 and PmPy–ZrO2 hybrids were analyzed by XPS, FTIR, XRD and UV–Vis techniques. To explore the advantages of these nanocomposites for potential applications, their thermal, conductive and electrochemical properties were investigated. The characterization reveals that a chemical bonding, based on electrostatic interactions, is established between the polymers and the ZrO2 nanoparticles. Interestingly, it is found that the growth of polymer on the surface of Cl-functionalized ZrO2 becomes more significant as the Py moiety (–NH– species) content in the polymer increases. The thermal stability and conductivity of the polymers increase by hybridization with the ZrO2 nanoparticles. This is assigned to the affective interaction of the polymers with the ZrO2 nanoparticles. Particularly, the resulting nanocomposites keep high conductivities, ranging between 0.323 and 0.929 S cm−1. Finally, voltammetric characterization shows that the PPy–ZrO2 and poly(Py-co-mPy)–ZrO2 nanocomposites are electroactive, thus demonstrating their capability for electrochemical applications. These results highlight the great influence of the nanoparticle interface and the nature of monomer on the nanocomposite formation and properties.

  相似文献   

18.
The electroactive copolymer of poly(acryloyl chloride) (PAC) and polypyrrole (PPy) can be synthesized by electrochemical polymerization using a polymer precursor which contains a pyrrole moiety in its side chain. Poly(acryloyl pyrrole) (PAP) was synthesized chemically with acryloyl chloride and potassium pyrrole salt and characterized using FT‐IR and 1H‐NMR spectroscopy. PAP dissolved in dimethyl formamide (DMF), was spin‐coated on a platinum electrode and polymerized electrochemically in the electrolytic mixture solution consisting of acetonitrile, 0.1 M pyrrole, and 0.1 M lithium perchlorate. Constant potential electrolysis showed that pyrrole groups in the precursor were oxidized to form PPy, that is, they acted as grafting centers at which the PPy grew. Scanning electron microscopy (SEM) results and conductivity measurements supported the formation of the graft copolymer. The morphological feature of PAC‐g‐PPy copolymer films showed homogeneous structure, but that of PAC/PPy composite films showed irregular structure. The maximum conductivity of the final products was about 1 S/cm. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

19.
《Solid State Sciences》2012,14(8):1238-1243
High performance PPy/PEG-LiFePO4 nanocomposites as cathode materials were synthesized by solvothermal method and simple chemical oxidative polymerization of pyrrole (Py) monomer on the surface of LiFePO4 particles. The samples were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectrometry (XPS) and charge-discharge tests. PPyPEG hybrid layers decrease particle to particle contact resistance while the impedance measurements confirmed that the coating of PPy-PEG significantly decreases the charge transfer resistance of the electrode material. The initial discharge capacities of this sample at C/5 and 1C are 150 and 128 mAh/g, respectively. The results show that PPy/PEGLiFePO4 composites are more effective than bare LiFePO4 as cathode material.  相似文献   

20.
Electropolymerization of pyrrole‐3‐acetic acid was performed by cyclic voltammetry on titanium and Ti90Al6V4 substrates with the aim of developing a multilayer structure for applications in advanced biomaterials. The polymeric films obtained were characterized by both XPS and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Information on the poly(pyrrole‐3‐acetic acid) (PPy‐3‐acetic) surface structure was achieved by a detailed XPS analysis of C 1s and N 1s signals. The number of COOH groups was quantified by XPS coupled to a chemical derivatization reaction in which esterification with trifluoroethanol was exploited so that the presence of fluorine (or the CF3 component in C 1s spectra) could be used as a marker for COOH groups. As a result, it was found that more than 90% of the monomer units along PPy‐3‐acetic chains bear carboxylic functionalities, of which 60% are protonated and 40% are present as carboxylate groups. Some decarboxylation occurs with film ageing. The PPy‐3‐acetic films were also investigated by ToF‐SIMS in the negative ion mode, thus obtaining, for the first time, interesting information on the structure of the top surface layers of a polymer belonging to the polypyrrole family. In particular, clusters of peaks related to PPy‐3‐acetic oligomers were detected and the decarboxylation phenomenon on top of the polymer surface was confirmed. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

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