A composite of polyaniline with both conducting and ferromagnetic functions

A composite of polyaniline (PANI) with both conducting and ferromagnetic functions was synthesized by a chemical method proposed by the authors. For the electrical properties, its room-temperature conductivity was measured to be about 10⁻¹ S/cm when doped with 1.0M HCl, and it is independent of the preparation conditions, such as reaction temperature and concentration of FeSO₄ solution. Temperature dependence of the conductivity of the composites at temperature between 77 and 450 K is controlled by thermal activation and dedoping processes, which result in the decrease of conductivity with increase of temperature as T > 320 K. For their magnetic properties, unusual ferromagnetic properties with high saturated magnetization (M₂) and lower coercive force (H_c = 0) were observed. An effect of the preparation conditions on the ferromagnetic properties of composites was observed. The higher the reaction temperature and the concentration of FeSO₄ solution, the higher the saturated magnetization was observed. No hysteresis feature (i.e. H_c = 0) for any PANI composites synthesized in this paper was observed, and this is independent of the preparation conditions. This may be attributed to the nanometer size of the magnetic particles existing in composites. Thus, it suggests that the doping of PANI leads to electrical properties of composites, whereas the nanocrystalline magnetic particles (Fe₃O₄) are responsible for the observed ferromagnetic properties of PANI composites. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2129–2136, 1997     

Chemical and electrochemical characterization of chemically synthesized conducting polypyrrole

The conducting polypyrrole chemically synthesized in water, using the variable concentrations of FeCl₃ and CuCl₂ as oxidizing agents, was chemically and electrochemically characterized and compared with electrochemically generated polypyrrole. According to the results of elemental analysis and counter ion determinations, it can be concluded that a mixture of dimer and trimer was obtained using CuCl₂, i.e., a dimer composition using FeCl₃ as an oxidant. Cyclic voltammetric studies of polypyrrole obtained by using FeCl₃ as an oxidant showed no evidence of polypyrrole decomposition after repetitive cycling. The voltammograms showed also that after the oxidation reaction a high capacitive current remained, confirming the assumption that the capacitive current is intrinsically associated with polypyrrole, irrespective of the way of its preparation. Cyclic voltammogram of the polypyrrole synthesized by oxidation with CuCl₂ showed different shape, probably influenced by the presence of copper ions incorporated in polymers. © 1992 John Wiley & Sons, Inc.     

导电聚吡咯纳米线的电化学无模板法可控合成与表征

以β-萘磺酸(NSA)为掺杂剂,采用电化学无模板法制备了聚吡咯(PPy)纳米线.研究了NSA浓度、吡咯(Py)单体浓度及反应温度对PPy纳米线形貌的影响.分别采用场发射扫描电子显微镜(FE-SEM)和拉曼光谱对PPy纳米线的结构形貌和化学结构进行了表征.结果表明,利用电化学无模板法可得到中空的PPy纳米线;NSA浓度会影响PPy纳米线的取向性;增大Py单体浓度,可制得圆锥状PPy纳米线;低温有利于合成形状细长、紧密堆积的PPy纳米线.PPy纳米线形貌受游离Py浓度及Py-NSA胶束数量影响,通过调节NSA浓度、Py浓度及反应温度改变游离Py浓度及Py-NSA胶束数量,可制得不同形貌的PPy纳米线.     

Influence of HCL on polypyrrole films prepared chemically from ferric chloride

Smooth, adherent films of the electrically conducting polypyrrole formed on surfaces in contact with unstirred aqueous solutions containing the pyrrole monomer and the oxidant, FeCl₃. Contradictory reports in the literature concerning the influence of HCl on the growth rate and electrical conductivity of polypyrrole grown in this manner prompted this study of the growth rate and conductivity of films. With no intentional addition of HCl, the growth rate of the films, measured using a quartz crystal microbalance, was fit to a simple second-order model in which the rate was limited by the bulk depletion of reactants. The conductivity of the films was found to be about 1 S cm^?1. Both the growth rate and the electrical conductivity initially increased with the deliberate addition of HCl to the solution. The conductivity was found to peak at a value about 20 S cm^?1 at an initial HCl concentration of 0.3 M. At initial HCl concentration of 2M or more, films could not be grown. © 1994 John Wiley & Sons, Inc.     

Synthesis of conducting polypyrrole by radiolysis polymerization method

Conducting polypyrrole (PPy) has been synthesized by the in situ gamma radiation‐induced chemical oxidative polymerization method. This method takes advantages of the specialties of radiation‐induction, and a highly uniform polymer morphology was obtained. The resultant nanosize polypyrrole particles were characterized by Elemental Analysis, Fourier transform infrared (FT‐IR), scanning electron microscope (SEM), transmission electron microscopy (TEM) and X‐ray Diffraction (XRD). Measurements of polymer particle sizes were obtained at <500 nm. A standard four‐point probe revealed that the chemical synthesis of PPy has a good electrical property. Also thermal stability, checked by Thermal Gravimetric Analysis in air, was ensured by this novel synthesis. Copyright © 2007 John Wiley & Sons, Ltd.     

Thermoelectric power and conductivity of different types of polypyrrole

We have measured the thermoelectric power and conductivity as a function of temperature of a wide range of polypyrrole samples, including a film of soluble polypyrrole synthesized chemically, and wrinkled films synthesized using indium–tin oxide electrodes; other samples investigated include high‐conductivity polypyrrole films synthesized at different temperatures and current densities, films grown on nonconducting substrates, and polypyrrole gas sensors. The thermoelectric powers are remarkably similar and metal‐like for the medium and high conductivity samples but show nonzero extrapolations to zero temperature for wrinkled samples. The temperature dependence of conductivity tends to be greater for samples of lower conductivity. In contrast to polyaniline and polyacetylene, a crossover to metallic sign for the temperature dependence of conductivity at higher temperatures is not observed in any of our samples; the fluctuation‐induced tunnelling and variable‐range hopping expressions account for nearly all our conductivity data except for low‐temperature anomalies. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 953–960, 1999     

Electrical and mechanical properties of the zone-drawn polypyrrole films

The zone-drawing method (ZD) was applied to electrochemically synthesized polypyrrole films containing tosylate (PPy/TsO) and the mechanical and electrical properties of the resulting films were investigated. It was found that the electrical conductivity of the zone-drawn film reached 365 S cm⁻¹ in the drawing direction, which was 4.7 times that of the original film. The tensile properties of the zone-drawn film were improved and Young's modulus and strength at break increased to 4.32 GPa and 90.1 MPa from 0.53 GPa and 40.4 MPa of the as-synthesized film, respectively. The dynamic storage modulus (E) increased by the zone-drawing over a whole experimental temperature range and attained 7.0 GPa at room temperature and 4.0 GPa even at 200°C. © 1996 John Wiley & Sons, Inc.     

Study on the preparation and multiproperties of the polypyrrole films doped with different ions

Conducting polypyrrole (PPy) films doped with p‐toluene solfonate (pTS^?), perchlorate (ClO₄^?) and polyphosphate (PP^?) were electrochemically synthesized on the stainless steel SS‐304 and the Indium Tin Oxide (ITO) glass substrates successfully. The conducting polymer composite films were studied by Fourier transform infrared spectra, integrated thermal analysis system and scanning electron microscopy, respectively. Four‐point probe measurements and in situ nanotribolab system equipped with a nanoscale electrical contact resistance package were employed to analyze their electrical and mechanical properties. Results indicate that the film doped with PP^? ion showed the best thermal stability. For the ClO₄^? ion doped films, the glass transition occurred at 274.8 °C. The pTS^? ion doped film on the SS‐304 steel had a good conductivity, and there was a voltage barrier that ranged from ?1.25 to 1.9 V according to the current–voltage curves. Nanoindentation tests show that the mechanical properties of the PPy/pTS^? film and the PPy/PP^? film were better than that of PPy/ClO₄^? films. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of preparation temperature on the conductivity of polypyrrole conducting polymer

An attempt has heen made to investigate the effect of temperature on the conductivity of polypyrrole conducting polymer films prepared by an electrochemical method in an aqueous medium using camphor sulfonate as the dopant. The polymer was grown from aqueous solutions employing a range of temperatures (l–60°C). It was found that with increase in temperature the conductivity decreased and the optimum temperature was found to be between 10 and 30°C. The results showthatthe polymer formed at low temperature has higher conductivity and is stronger than that formed at higher temperatures. Characterization by X-ray scattering shows that interlayer distance, d_Bragg (?), increases with increasing temperature. The morphology of the films formed was studied by using a scanning electron microscope (SEM). The changes in conductivity and physical appearance were interpreted as being due to compactness in the molecular packing and formation ofαβ linkages in the film.     

Synthesis of a hexafluoropropylidene-bis(phthalic anhydride)-based polyimide and its conducting polymer composites with polypyrrole

A new electrically conducting composite film from polypyrrole and 4,4′-(hexafluoroisopropylidene)-bis(phthalic anhydride)-based polyimide was prepared. Pyrrole and the dopant ion can easily penetrate through the polyimide substrate and electropolymerize on the platinum (Pt) electrode due to the swelling of the polyimide on the metal electrode. The electrochemical properties of polypyrrole-polyimide (PPy/PI) composite films have been investigated by using cyclic voltammetry. The PPy/PI composite film is suitable for use as the electroactive material owing to its stable and controllable electrochemical properties. The electrical conductivity of composites falls in the range 0.0035–15 S/cm. Scanning electron micrograph, FTIR, and thermal studies indicate that PPy and PI form a homogeneous material rather than a simple mixture. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3009–3016, 1997     

Synthesis and characterization of polypyrrole nanofibers with different dopants

Nanostructures of polypyrrole (PPy) were synthesized in the presence of different dopants including hydrochloric acid (HCl), ferric chloride (FeCl₃), p‐toluene sulfonic acid (p‐TSA), camphor sulfonic acid (CSA), and polystyrene sulfonic acid (PSSA), using a simple interfacial oxidative polymerization method. The method is a reliable non‐template approach with relatively simple instrumentation, ease of synthesis, and economic viability for synthesizing PPy nanostructures. Morphology of synthesized PPy structures was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which indicate the formation of one‐dimensional (1D) nanofibers with average diameter of 75–180 nm. Energy dispersive spectrum (EDS) of the PPy nanofibers indicates the attachment of the dopants to the PPy backbone; the fact is further confirmed by the Fourier transform infrared (FTIR) spectra of PPy nanostructures. Thermal stabilities of the nanostructures explored using thermal gravimetric analysis (TGA) follow the order PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA. It is noticed that the electrical conductivity (EC) of PPy nanostructures depends upon the nature of dopant (PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA), PPy‐p‐TSA nanofibers showing the highest EC of 6 × 10^?2 Scm^?1. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermal diffusivity and electrical conductivity of electropolymerized polypyrrole films

This article presents measurement of thermal diffusivity and electrical conductivity of polypyrrole films prepared by electropolymerization. Thermal diffusivity was measured by laser radiometry (former flash radiometry). Electrical conductivity was determined by a conventional four-probe method. Increase of thermal diffusivity is observed when increasing the supporting electrolyte concentration, which is also shared with the increase of electrical conductivity. Both thermal diffusivity and electrical conductivity significantly depended on the types of counter anion incorporating into polymer bulk. Thermal diffusivity of polypyrrole film is larger than that for common nonelectrical conductive polymers. Temperature profile of thermal diffusivity for as-grown polypyrrole films shows that thermal diffusivity increases with increasing temperature (first running profile), whereas remeasured temperature profile of thermal diffusivity (second or third running profiles) shows the decrease of thermal diffusivity with increasing temperature. Electrical conductivity monotonically increases until the significant decrease of it occurs at the temperature above 130°C. Investigation of these temperature profiles of thermal diffusivity and electrical conductivity has been made by corresponding to thermal analysis data. © 1994 John Wiley & Sons, Inc.     

Conductivity relaxation behavior of interpenetrating polymer network composites of polypyrrole and poly(styrene‐co‐butyl acrylate)

Conductivity relaxation spectra of interpenetrating network conducting composites of polypyrrole (PPy) and poly(styrene‐co‐butyl acrylate) (SBA) have been analysed on the basis of coupling model developed by Ngai. The macroscopic activation energy obtained from coupling model using the stretch exponent β compares favourably with the tunnel energy estimated from the overlapping large polaron tunnelling (OLPT) model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1193–1200, 2000     

Preparation and characterization of polypyrrole/magnetite nanocomposites synthesized by in situ chemical oxidative polymerization

This work describes the preparation and characterization of polypyrrole (PPy)/iron oxide nanocomposites fabricated from monodispersed iron oxide nanoparticles in the crystalline form of magnetite (Fe₃O₄) and PPy by in situ chemical oxidative polymerization. Two spherical nanoparticles of magnetite, such as 4 and 8 nm, served as cores were first dispersed in an aqueous solution with anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate to form micelle/magnetite spherical templates that avoid the aggregation of magnetite nanoparticles during the further preparation of nanocomposites. The PPy/magnetite nanocomposites were then synthesized on the surface of the spherical templates. Structural and morphological analysis showed that the fabricated PPy/magnetite nanocomposites are core (magnetite)‐shell (PPy) structures. Morphology of the PPy/magnetite nanocomposites containing monodispersed 4‐nm magnetite nanoparticles shows a remarkable change from spherical to tube‐like structures as the content of nanoparticles increases from 12 to 24 wt %. Conductivities of these PPy/magnetite nanocomposites show significant enhancements when compared with those of PPy without magnetite nanoparticles, in particular the conductivities of 36 wt % PPy/magnetite nanocomposites with 4‐nm magnetite nanoparticles are about six times in magnitude higher than those of PPy without magnetite nanocomposites. These results suggest that the tube‐like structures of 36 wt % PPy/magnetite nanocomposites may be served as conducting network to enhance the conductivity of nanocomposites. The magnetic properties of 24 and 36 wt % PPy/magnetitenanocomposites show ferromagnetic behavior and supermagnetism, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1291–1300, 2008     

Effect of ammonia on the temperature‐dependent conductivity and thermopower of polypyrrole

We report the first measurements of the effect of ammonia gas on the temperature dependence of the conductivity and thermoelectric power of polypyrrole films. Our data are for samples of very different conductivities, extending down to a temperature of 200 K for low‐conductivity polypyrrole gas sensors, and down to 4.2 K for more highly‐conducting PPy(PF₆) samples. We demonstrate that (except for the most metallic case) our polypyrrole samples show greater sensitivity to ammonia as the temperature is lowered (i.e. the fractional reduction in conductivity is greater at lower temperatures). Remanent decreases in conductivity are present after the removal of ammonia for higher pressure exposures, and remanent increases in the metal‐like thermoelectric power for the PPy(PF₆) for samples grown at higher temperatures. Our results indicate that the mechanism of this conductivity decrease in PPy(PF₆) is that ammonia causes a reduction in the size of metallic regions as disordered barrier regions are thickened. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1331–1338, 2006     

Synthesis and Characterization of Polyvinylferrocene/Polypyrrole Composites

Conducting polymer composites of polyvinylferrocene and polypyrrole (PVF/PPy) were synthesized chemically by the in situ polymerization of pyrrole in the presence of PVF using FeCl₃ as oxidant. Acetic (CH₃COOH) and boric (H₃BO₃) acids were used as the synthesis medium. Effects of the synthesis medium on the properties of the PVF/PPy composite were investigated. The PVF/PPy composites and homopolymers were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and magnetic susceptibility techniques. Conductivity measurements were performed using the four‐probe technique. We found that the conductivities of PVF/PPy‐H₃BO₃ (1.19 S cm^?1) and PVF/PPy‐CH₃COOH (4.5×10^?1 S cm^?1) increased relative to those of the homopolymers of PPy‐H₃BO₃ (2.1×10^?2 S cm^?1) and PPy‐CH₃COOH (1.2×10^?2 S cm^?1) due to the interaction of PVF with the pyrrole moiety. The stability of all homopolymers and composites were investigated by thermogravimetric analysis and by conductivity measurements during heating‐cooling cycles. There was a small drop in conductivity caused by the annealing of PVF/PPy composites at 70°C. The conductivity of all samples increased with temperature and exhibited stable electrical behavior with increasing temperature. TGA analysis of samples showed that the composites were more stable than the homopolymers or PVF separately. The magnetic susceptibility values of samples were negative, except for PVF/PPy‐H₃BO₃. Morphology changes of the composites investigated by scanning electron microscopy (SEM), attributed to synthesis conditions, have a significant effect on their conductivity.     

In situ intercalative polymerization of conducting polypyrrole/montmorillonite nanocomposites

Conducting polypyrrole (PPy)‐montmorillonite (MMT) clay nanocomposites have been synthesized by the in situ intercalative polymerization method. The PPy‐MMT nanocomposites are characterized by field‐emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, thermogravimetric analysis (TGA), and Fourier‐transform infrared (FTIR) spectroscopy. XRD patterns show that after polymerization by the in situ intercalative method with ammonium persulfate and 1 M HCl, an increase in the basal spacing from 1.2 to 1.9 nm was observed, signifying that PPy is synthesized between the interlayer spaces of MMT. TEM and SEM micrographs suggest that the coexistence of intercalated MMT layers with the PPy macromolecules. FTIR reveals that there might be possible interfacial interactions present between the MMT clay and PPy matrix. The study also shows that the introduction of MMT clay results in thermal stability improvement of the PPy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2279–2285, 2008     

Preparation, characterization, and adhesion of monodispersed polypyrrole particles

Uniform colloidal polypyrrole particles ranging from 17 to 59 nm in diameter were prepared by the oxidation of pyrrole with sodium persulfate in the presence of the nonionic Rhodasurf TB970 polymeric stabilizer and 4-ethyl benzenesulfonic acid. The adhesion of these particles on glass beads was studied as a function of the pH using the packed column technique. Polypyrrole was found to deposit on glass only at pH values below its isoelectric point (i.e.p.), forming a monolayer. The entire amount of the adhered polypyrrole could be rapidly removed by rinsing the column with 1×10^-2 mol dm^-3 NaOH solution. Received: 3 April 1998 Accepted: 27 April 1998     

过渡金属一取代Keggin结构钼磷酸盐掺杂的聚吡咯的制备、表征与导电性研究

０引言有机高分子－多酸导电聚合物是８０年代末兴起的一类新型有机－无机杂化材料。由于它兼有无机组分和有机聚合物基块的性能，并能衍生出新的导电性、光学性、耐摩擦、力学性能、功能梯度等，它现已成为材料科学和化学科学研究的前沿课题之一犤１犦。多酸是一类含有氧桥的多核配合物，具有强酸性、强氧化性、优良的催化活性、光致变色、电致变色性及高质子导电性等，可作为构建有机－无机杂化材料的基块犤２，３犦。聚吡咯是一类有机高分子，其合成简便、空气稳定性好、易于掺杂，通过掺杂可形成高电导率的高分子材料。若将多酸掺杂聚吡…     

Synthesis and characterization of polypyrrole dispersions prepared with different dopants

Stable polypyrrole dispersions were prepared by chemical oxidative polymerization of pyrrole in an aqueous medium containing different anionic salts - sodium benzoate, potassium hydrogen phthalate and sodium hydrogen succinate. Results of the elemental analysis and FT-IR spectroscopy confirmed that the anionic salts are incorporated in the conducting polymers and functioned as the dopants. The retardation of pyrrole polymerization was observed when a certain amount of the salt was used as dopant. SEM images of polypyrrole dispersions indicate large spherical particles (150-180nm). The conductivity of polypyrrole composites has also been investigated.