Preparation of polypyrrole/polythiophene double layers by electrochemical polymerization of pyrrole in the presence of thiophene

Studies on electrochemical polymerization of pyrrole in the presence of thiophene are given for preparation of polypyrrole (PPy)/polythiophene (PTh) double layers. At a constant current, only pyrrole is electrochemically polymerized in the electrolytic solution containing pyrrole and thiophene in the present experiments. The cyclic voltammograms on pyrrole/thiophene mixtures are similar to that on pyrrole. Preparation of PPy/PTh double layers is carried out by electrochemical polymerization of pyrrole in the presence of thiophene by adding pyrrole and by lowering voltage immediately after electrochemical homopolymerization of thiophene. The resulting double layers show good rectification characters dependent on thickness. © 1995 John Wiley & Sons, Inc.     

Copolymer from electropolymerization of thiophene and 3,4-ethylenedioxythiophene and its use as cathode for lithium ion battery

Electropolymerizations (EPs) of thiophene (Th), 3,4-ethylenedioxythiophene (EDOT) and the mixed monomers of Th and EDOT in 0.05 M Et₄NClO₄/propylene carbonate (PC) solution were performed to prepare polymer films as potential cathode materials in lithium ion battery. The incorporation of EDOT units into pure polythiophene (PTh) chain leads to large alternations on the experimental conditions of EPs and the properties of the resulting polymer films. Onset potential of the EPs was reduced with the participation of EDOT component. The resulting polymers, PTh, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(thiophene-co-3,4-ethylenedioxythiophene) (PTh-EDOT) were then served as cathode materials to test their capabilities to transport lithium ion in 1.0 M LiPF₆/ethylene carbonate/dimethyl carbonate solution. With the inherent EDOT unit, PEDOT and PTh-EDOT have better charge capacity, stability and response rate than pure PTh. Among the copolymers, PTh-EDOT (1/1) even shows better stability than pure PEDOT homopolymer, advantage of using EDOT as copolymer component is thus evaluated.     

In situ polymerizations of thiophene on TiO2 films using the semiconductors as initiators

In this work, we prepare the TiO₂ nanoparticle film and anatase TiO₂ nanoarray film, and we achieve the polymerizations of thiophene using the photoexcited TiO₂ film as the initiators. It is measured that the in situ polymerizations of thiophene take place on the surfaces of the two films. The growth of polythiophene (PTh) on the TiO₂ nanoarray is monitored using Fourier‐transform Raman spectroscopy. The TiO₂ nanoarray is found to strongly interact with the PTh polymers. It is observed using scanning electron microscope that the microspores in the nanoarray are filled by the polymers after the reaction of 3 h, and the nanoarray is fully covered by the polymer layer when the polymerization lasts for 5 h. The PTh–TiO₂ nanoarray composite films are measured for the transient photocurrents and photocurrent‐voltage characteristics. The dependence of the photocurrents on the reaction time is revealed and discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40187.     

Synthesis and characterization of high temperature resistance interpenetrating polymer network

Interpenetrating polymer network (IPN) polymer has been prepared by blending silicone resin polymer with the organic polymers such as polypyrrole [PPy] and polythiophene [PTh]. The IPNs were characterized by FTIR, NMR, and TGA/DSC analysis. The heat resistance performance of these IPNs were evaluated as per ASTM D2485. The result indicates that the IPN based on silicone‐PTh has got superior heat resistant property than silicone‐PPy. The electrochemical impedance measurements showed that the corrosion resistances of both the IPNs was similar. AFM morphological study confirms the influence of PPy/PTh on silicone polymer in forming smooth heterogeneous micro‐structured IPNs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pyrrole Electropolymerization on Copper and Brass in a Single-Step Process from Aqueous Solution

The electrosynthesis of polypyrrole (PPy) on copper and brass (Cu–Zn alloy) electrodes was performed by anodic oxidation of pyrrole in a sodium tartrate (C₄H₄Na₂O₆ 0.2 M) aqueous solution. The tartrate counter-ions slow the dissolution of the working electrode by leading to formation of a passivation layer on its surface, and pyrrole electropolymerization takes place. Strongly adherent and homogeneous polypyrrole films were electrodeposited on Cu and Cu–Zn alloy electrodes using different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. The current densities of electropolymerization on brass are generally greater than those observed on copper. The corrosion behaviour of copper-coated electrodes, electrochemically modified by PPy films, was estimated by DC polarization and weight loss at different current densities in 0.1 M HCl solution. The synthesized polypyrrole films were characterised by several microscopic and spectroscopic techniques such as scanning electron microscopy, X-ray photo electron spectroscopy, Fourier transform infrared and Raman analysis. Galvanostatically deposited PPy films are shown to be an alternative to common black-nickel or black-chromium as a decorative top-coating.     

Coatings of Conducting Polymers for Corrosion Protection of Mild Steel

The investigation of electrochemical behavior of different conducting polymers, polythiophene (PTh), polypyrrole (PPy) and polyterthiophene (PTTh) on a mild steel (MS) electrode were done. Moreover, the combinations of the conducting polymers PTh and PPy was investigated. The synthesis of all polymeric coatings was done by the cyclic voltammetry technique. The electrochemical impedance spectroscopy (EIS) measurements were used to evaluate the corrosion performance of coated mild steel by different polymers in 0.5 M of different acid solutions (HCl, HClO₄, H₂ C ₂ O ₄, H₃PO₄ and HNO₃). The protection of all polymeric coatings against corrosion of the substrate was promising and the bilayer coating PPy/PTh gave the best protection efficiency in all used acids. The order of efficiency for the different coatings in HCl and HNO₃ solutions was MS/PPy/PTh > MS/PPy > MS/PTTh > MS/PTh but the order in HClO₄, H₃PO₄ and H₂ C ₂ O ₄ solutions was MS/PPy/PTh > MS/PTTh > MS/PPy > MS/PTh.     

Polythiophene, polyaniline and polypyrrole electrodes modified by electrodeposition of Pt and Pt+Pb for formic acid electrooxidation

The electrosynthesis of polythiophene (PTh), polyaniline (PANI) and polypyrrole (PPy) films modified by dispersion of Pt or Pt+Pb and its employment in the electrocatalytic oxidation of HCOOH are studied and compared. The influence of parameters such as polymer film thickness, the number of dispersed Pt particles, the amount of Pb deposited and the presence of Pb2+ in the electrolyte on the electrooxidation of HCOOH is investigated. Electrode systems including the polymer and a mixture of Pt and Pb particles show a better electrocatalytic activity than electrodes having a polymer–Pt combination or bulk Pt electrodes. Furthermore, during the electrooxidation of HCOOH using polymer–(Pt+Pb) electrodes the presence of fewer poisoning species is observed, indicating that the role of Pb in these electrode systems is in agreement with the Pb adatom effect observed when bulk Pt electrodes are used. However, the presence of Pb(ii) in the electrolyte is not required for the PTh–(Pt+Pb) electrode system and, in addition, a better electrocatalytic effect is obtained in this case. With application of an appropriate E/t program the activity is unchanged over a long time.     

Modification of polythiophene by the incorporation of processable polymeric chains: Recent progress in synthesis and applications

Intrinsically conductive polymers (ICPs) have attracted significant attention in recent decades because of their wide range of potential applications in various fields such as chemistry, physics, electronics, optics, materials, and biomedical sciences. In particular, conjugated polythiophene (PTh) and its derivatives stand out as the most promising members of the conjugated polymer family because of their unique electrical behavior, excellent environmental and thermal stability, low-cost synthesis, and mechanical strength. However, similar to other π-conjugated polymers the main drawback of unsubstituted PTh is the lack of solubility due to its strong interchain interactions, resulting in limited processability. Various procedures have been invoked to overcome these restrictions, such as side chain functionalization, the synthesis of PTh copolymers with processable polymers, and combination of both of these strategies. Because of large number of publications on the chemical modification of polythiophene, this review is focused on progress in the synthesis of polythiophene copolymers with processable polymers. The properties of the polythiophene copolymers and their applications are also highlighted.     

Electrochemical copolymerization and stability of crosslinked bis[1,2‐(pyrrol)ethoxy]ethane with pyrrole

The copolymers, pyrrole‐co‐bis[1,2‐(pyrrol)ethoxy]ethane (PEE), were produced by electropolymerization in acetonitrile (containing 0.1 mol L⁻¹ lithium perchlorate). The properties and morphology of these polymers were investigated by cyclic voltammetry, UV–vis absorption spectra and scanning electron microscopy (SEM), respectively. The results exhibit that the cyclic voltammograms and rates of electropolymerization of the prepared copolymers were significantly affected by PEE concentration in water and acetonitrile solution. Higher applied potential was required for the polymerization with decreasing the ratio of pyrrole/PEE. This was ascribed to the steric hindrance of high concentration of N‐substituted groups. The SEM images of the poly(pyrrole‐co‐PEE) and PPEE films show more compact and more smooth morphology compared with that of PPy and cyclic voltammogram of the poly(pyrrole‐co‐PEE) films, which display good electrochemical stability in the mixed solution, indicating that the modification of crosslinked structure was effective for the stabilization of the redox cycles. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Porous palygorskite‐polythiophene conductive composites for acrylic coatings

Modified palygorskite‐polythiophene (MPA‐PTh) composites were prepared by chemical oxidative polymerization of palygorskite (PA) nucleartor with thiophene (Th) after the surface modification with γ‐(2,3‐epoxypropoxy) propytrimethoxysilane (KH‐560). The MPA‐PTh composites were doped in iodine vapor to create the porous palygorskite‐polythiophene (PMPA‐PTh) conductive composites. Fourier transform infrared spectra (FTIR), X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption–desorption isotherms using the Brunauer–Emmett–Teller method (BET) and electrochemical impedance spectrum (EIS) techniques were applied to characterize the modified PA and the prepared composites. According to FTIR and XPS, the KH‐560 was bound to the PA surface and the iodine ion (I₃^? and I₅^?) entered the PTh molecular chains. XRD, SEM, TEM, BET, and EIS analysis confirmed that the doping of iodine not only transform the core–shell MPA‐PTh into the PMPA‐PTh but also improve the electrical conductivity of composites. The PMPA‐PTh composites were fabricated that yield a volume resistivity of ～2.44 × 10² Ω cm and a internal resistances of ～100 Ω, and their BET surface area, BJH (Barrett–Joiner–Halenda) average pore size and BJH cumulative pore volume were improved in comparison with those of the MPA‐PTh composites. SEM images showed that the PMPA‐PTh composites could form consecutive space network and the PMPA‐PTh composites acrylic coating films had advisable conductivity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The morphology and conductivity of polypyrrole/polyurethane alloy films

Polymeric composites with conductivities ranging from 10^–4 to 1 S cm^–1 were prepared by electrochemically polymerizing pyrrole in a matrix of polyurethane. The polypyrrole/polyurethane alloy films obtained were characterized by element analysis, electron microscopy and electrical conductivity measurements. The morphology of the films depended on the solvent, the electrolyte and the current density. The mechanism of the electrochemical polymerization showed that PPy grew in a treelike structure, with molecular chains extending from the electrode surface into the solution. The transition temperature of the PPy/PU increased with the PPy content.     

High-performance polymer/nanodiamond composites: synthesis and properties

Conjugated polymer/nanodiamond nanocomposites have been known as high-performance materials due to improved physical properties relative to conventional composites. In this attempt, novel conjugated polymer/nanodiamond nanocomposites were successfully prepared by in situ oxidative polymerization. Physical characteristics of the resultant nanocomposites were explored using Fourier transform infrared spectroscopy, field emission scanning electron microscope (FESEM), energy dispersive X-ray spectroscope, differential scanning calorimeter, thermogravimetric analysis and X-ray diffraction spectroscopy. Structural analysis revealed the oxidative polymerization of various matrices [polyaniline (PANi), polypyrrole (PPy), polythiophene (PTh) and polyazopyridine (PAP)] over the surface of functionalized (F-NDs) and non-functionalized nanodiamonds (NF-NDs) thus ensuing NF-NDs/PAP/PANi/PPy, F-NDs/PAP/PANi/PPy, NF-NDs/PANi/PPy/PTh and F-NDs/PANi/PPy/PTh nanocomposites. FESEM images depicted the fibrillar morphology of resulting nanocomposites with granular arrangement of nanofiller in matrix. Thermal analysis results showed that the functionalized F-NDs/PAP/PANi/PPy hybrid had higher value of 10 % weight loss around 489 °C relative to F-NDs/PANi/PPy/PTh with T₁₀ at 471 °C. The glass transition temperature was found to be 99 and 105 °C for NF-NDs/PANi/PPy/PTh and F-NDs/PANi/PPy/PTh, respectively. On the other hand, NF-NDS/PAP/PANi/PPy and F-NDs/PAP/PANi/PPy showed higher T _g’_s of 109 and 118 °C. The conductivity of NF-NDs/PAP/PANi/PPy was 3.8 Scm^?1 and improved with the functionalized filler loading in F-NDs/PAP/PANi/PPy up to 5.4 Scm^?1, while NF-NDs/PANi/PPy/PTh and F-NDs/PANi/PPy/PTh had relatively lower values around 2.9 and 3.7 Scm^?1, respectively. New conducting nanocomposites may act as useful contenders in significant industrial applications such as polymer Li-ion battery.     

Electropolymerization and electrochemical properties of (N-hydroxyalkyl)pyrrole/pyrrole copolymers

In this study, the N-hydroxyalkyl derivatives of pyrrole (Py), N-(2-hydroxyethyl)pyrrole (HE) and N-(3-hydroxypropyl)pyrrole (HP), were synthesized. The corresponding homopolymers, PHE and PHP, together with the copolymers of Py/HE and those of Py/HP were prepared by galvanostatic polymerization. These monomers and polymers were characterized by FTIR spectroscopy, elemental analysis, SEM and electrochemical techniques. The result of potential-time profiles showed that a higher potential was required for HE and HP than Py for the polymerization. This was ascribed to the steric hindrance of high concentration of the N-hydroxyalkyl groups. However, a similar potential was observed for the copolymerization of Py/HE and Py/HP systems as that of Py due to the reduction of the steric effect by lower content of the substituent. The SEM micrographs showed a rougher morphology for the films synthesized from the solutions with higher Py/derivatives ratio. The cyclic voltammograms indicated that all the copolymers were larger, while the homopolymers had smaller anodic/cathodic currents and specific charges than PPy. This implied that the existence of the proper amount of the N-hydroxyalkyl pendant groups enhanced the ionic mobility of the pyrrole polymers. The results of charge/discharge measurements showed that the copolymer PYHP82 has the highest discharge capacity among the pyrrole polymers prepared.     

Effect of the surface roughness of conducting polypyrrole thin-film electrodes on the electrocatalytic reduction of nitrobenzene

Conducting polypyrrole (PPy) thin-film electrodes were prepared by the electropolymerization of pyrrole on gold-coated glass plates. Films of various roughnesses were obtained by the variation of the scan rates during electropolymerization. These thin films were modified by doping with 6mM of the dopant NiCl₂. The surface morphology of the films was studied by scanning electron microscopy and atomic force microscopy (AFM), which suggested films prepared with a high scan rate were rougher in nature than the films produced with a low scan rate. The electrocatalytic reduction of nitrobenzene was carried out with these electrodes with the cyclic voltammetry technique in acetonitrile containing 0.1M HClO₄ as a supporting electrolyte. The various results obtained show that the conducting PPy thin-film electrodes were catalytically active toward the electroreduction process. The modified PPy film electrodes doped with NiCl₂ were more active toward nitrobenzene electroreduction than the PPy film alone. The results indicate that the roughness of the films played a very important role in determining their catalytic activity. The PPy films that were more rough in nature were catalytically more active than the smooth films; this may have been due to the availability of more reactive sites in the case of rough films. The apparent diffusion coefficients of the PPy film electrodes were also calculated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of thienyl‐ and terthienyl‐group‐bearing methacrylic polymers as precursors for grafting reactions of thiophene side‐chains

Acrylic and methacrylic monomers bearing pyrrolyl, thienyl and terthienyl groups, were synthesized and copolymerized with various amounts of butyl acrylate and butyl methacrylate. In the resulting copolymers the heterocycle side‐groups behaved as initiators in the oxidative polymerization of thiophene, allowing the polythiophene chains to grow from the side‐groups and leading therefore to graft copolymers. These last were collected mostly as insoluble fractions after extraction with chloroform. Processible polymers with polythiophene side‐chains were obtained when in the precursor polymer the heterocycle side‐group content was very low. The presence in the graft copolymers of a significant number of stiff polythiophene side‐chains was responsible for the rise in Tg values in comparison with the precursor polymers. The average number of grafted thiophene units, evaluated in the range 2–7.5, did not relate directly to measured conductivity values that were in the range 5.9 × 10⁻⁵–6.2 × 10⁻² S cm⁻¹. © 1999 Society of Chemical Industry     

Characteristics of electrochemically synthesized polymer electrodes in lithium cells—II. Polythiophene

The characteristics of electrochemically synthesized polythiophene electrodes have been examined in view of their application in rechargeable lithium, organic electrolyte batteries. The kinetics of the electrochemical doping process of polythiophene in LiClO₄-propylene carbonate electrolyte are quite fast, especially for polymers grown from the 2,2′-dithiophene dimer. The polythiophene electrodes behave very satisfactorily in terms of charge-discharge efficiency and cyclability. However, also this type of electrodes seems to be affected by the self-discharge processes commonly experienced by semiconducting polymers in lithium, organic electrolyte batteries.     

Characterization and Corrosion Protection Ability of Conducting Polymer Coatings on Mild Steel in Acid Media

Silicon - Electrochemical polymerization of polythiophene (PTh), polypyrrole (PPy) and polyterthiophene (PTTh) were investigated on mild steel (MS) electrode. Multilayered coating, consisting of...     

New single-step electrosynthesis process of homogeneous and strongly adherent polypyrrole films on iron electrodes in aqueous medium

Homogeneous and strongly adherent polypyrrole (PPy) films were electrochemically synthesized on iron electrodes in sodium tartrate (Na₂C₄O₆H₄ 0.2 M) aqueous solution. This one step pyrrole electropolymerization process has been successfully achieved under different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. During the first stage of the electrochemical process the tartrate counterion slows down the iron dissolution by leading to the formation of a passivation layer on the working electrode surface, and the pyrrole electropolymerization takes place. The electrosynthesized polymer deposit has been characterized by several microscopic and spectroscopic techniques. Any iron traces have been detected by X-ray photoelectron spectroscopy (XPS) on the outer side of the PPy films, which confirms the compactness and the homogeneity of the polymeric coating. Scanning electronic microscopy (SEM) imaging showed uniform and compact PPy coatings with cauliflower-like structure. Infra-red (IR) and Raman spectroscopies proved that the obtained PPy films have the same vibrational properties as those electrodeposited on noble Pt plates.     

Conducting polymers for corrosion protection: a review

Conducting polymers (CPs) such as polyaniline (PANI), polypyrrole (PPy), and polythiophene (PTh) are used for the corrosion protection of metals and metal alloys. Several groups have reported diverse views about the corrosion protection by CPs and hence various mechanisms have been suggested to explain anticorrosion properties of CPs. These include anodic protection, controlled inhibitor release as well as barrier protection mechanisms. Different approaches have been developed for the use of CPs in protective coatings (dopants, composites, blends). A judicious choice of synthesis parameters leads to an improvement in the anticorrosion properties of the coatings prepared by CPs for metals and their alloys. This article is prepared as a review of the application of CPs for corrosion protection of metal alloys.     

Conductive polyaniline–polythiophene/poly(ethylene terephthalate) composite fiber: Effects of pH and washing processes on surface resistivity

A conductive polyaniline (PAn)–polythiophene (PTh)/poly(ethylene terephthalate) (PET) composite fiber was prepared by polymerization of aniline and thiophene in the presence of PET fibers in an organic medium with FeCl₃. The effects of polymerization conditions, such as polymerization medium, mol ratios of aniline/thiophene and FeCl₃/aniline‐thiophene as well as polymerization temperature and time, were investigated on PAn–PTh content (%) and surface resistivity of the composite. The composite with the lowest surface resistivity (1.30 MΩ/cm²) was obtained by polymerization of aniline and thiophene (1/3 mol ratio) in acetonitrile/chloroform (1/5 volume ratio) at 20°C. The surface resistivity of the PAn–PTh/PET composite containing 4.8% PAn–PTh was increased from 1.9 MΩ/cm² to 270 MΩ/cm² at pH 11. The washing durability of the composites was determined with domestic and commercial laundering processes by monitoring the surface resistivity and morphology. The composite was also characterized with FTIR, TGA, elemental analysis, optic microscope and SEM techniques. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41979.