Characterization of polypyrrole films electrosynthesized onto titanium in the presence of sodium bis(2-ethylhexyl) sulfosuccinate (AOT)

Films of polypyrrole (PPy) were successfully electrosynthesized onto titanium in neutral and alkaline solutions of sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT or AOT) by potentiodynamic, galvanostatic and potentiostatic techniques. Results of the characterization of the films by cyclic voltammetry, scanning electron microscopy (SEM) and adhesion measurements are presented. It was found that the AOT molecule remains entrapped within the polymer matrix. The initial growth of the polymer produces electroactive toroidal deposits whereas for electropolymerization of longer duration the typical globular structure is developed. Adherence to Ti increases with deposition time and this result is interpreted as a consequence of the growth of a composite PPy/Ti oxide.     

Study of the anticorrosive properties of polypyrrole/polyaniline bilayer via electrochemical techniques

In this work, using electrochemical techniques the authors investigated the protective properties of a polypyrrole/polyaniline bilayer as a conductive polymer. A polypyrrole/polyaniline bilayer was deposited on carbon steel substrate by potentiostatic method. The electric capacitance and resistance of the films were monitored with the immersion time in a corrosive solution to investigate the water permeability of the films. Polypyrrole/polyaniline bilayer has a relatively low permeability and good catalytic behavior in passivation of carbon steel in longer periods. The results show that the bilayer has a better anticorrosive behavior compared to homopolymers (polypyrrole and polyaniline).     

Improvement of the anticorrosion properties of polypyrrole by zinc phosphate pigment incorporation

A commercial zinc phosphate pigment was incorporated into polypyrrole (PPy) matrix during its electrochemical synthesis in order to improve the corrosion protection of polypyrrole on AISI 1010 steel. PPy/zinc phosphate composite films were synthesised in sodium salicylate medium with high current efficiency and containing 10% by weight of zinc and 4% by weight of phosphate. The influence of stirring and concentration of the electrolyte on the degree of pigment incorporation were investigated, as well as polymerisation time and applied current density. The morphology of the films was determined by scanning electron microscopy (SEM) and the distribution of pigment in the polymeric matrix was carried out by X-ray photoelectron spectroscopy (XPS). The PPy and PPy/zinc phosphate films were submitted to salt spray corrosion test, weight loss test and to electrochemical measurements like corrosion potential with time. In all tests, the composite films showed an enhancement in its protective action in comparison with PPy films.     

Corrosion protection properties of polypyrrole electropolymerized onto steel in the presence of salicylate

The corrosion performance of a polypyrrole coating constituted by hollow rectangular microtubes was monitored in chloride solutions using open circuit potential measurements, potentiostatic polarization and electrochemical impedance spectroscopy. The coating was electrosynthesized onto 316 L stainless steel from a salicylate solution and it provided a very good corrosion resistance to the substrate. It was found that polypyrrole films with granular morphology electrodeposited from a salicylate solution with lower concentration behave better in terms of protective behavior. In order to improve the corrosion protection imparted by the polypyrrole coating formed by the microtubes a system of two layers was electrodeposited, the first one consisted of polypyrrole with a granular morphology and the second one, on the top, was constituted by the microtubes. This bilayered system exhibited an excellent protective behavior during considerably long immersion time.     

Polypyrrole films modified with graphite layer on mild steel

Electrochemically synthesized polypyrrole coating was modified with very thin graphite layer and top coated with another polypyrrole film. The corrosion behaviour of this coating has been investigated in aqueous sodium chloride solution. The synthesis of polypyrrole coatings was carried out by cyclic voltammetry technique, from aqueous oxalic acid solution. Electrochemical impedance spectroscopy and potentiodynamic measurements were used for corrosion tests. The cyclic voltammograms obtained in oxalic acid solution and the polarisation curves obtained in sodium chloride solution showed that the stability of coating was improved significantly by graphite layer. The impedance spectra also showed that the corrosion process was controlled by the diffusion rate along the coating, even after 96 h immersion period. The Warburg coefficient values were calculated and used to evaluate the barrier property of coating with time. It was shown that the water up taking process was slowed down by the hydrophobic nature of the graphite layer sandwiched between the two polypyrrole films.     

The corrosion-inhibiting effect of polypyrrole films doped with p-toluene-sulfonate,benzene-sulfonate or dodecyl-sulfate anions,as coating on stainless steel in NaCl aqueous solutions

This article presents a study of the conditions for electro-synthesis of polypyrrole (PPy) films on stainless steel, in the presence of the anions p-toluene-sulfonate (pTS), benzene-sulfonate (BS) or dodecyl-sulfate (DS). Cyclic voltammetry (CV) was used in the synthesis of the polypyrrole films on the stainless steel (SS). These polymeric films were characterized by IR and UV–vis spectroscopy and their morphology and thickness were analyzed by scanning electron microscopy (SEM). Their performance as protective films against corrosive processes presented by the SS/PPy-pTS, SS/PPy-BS or SS/PPy-DS systems was evaluated in 0.1 M NaCl aqueous solution. The study of the corrosion processes of the stainless steel/polymer systems was conducted through measurements of open circuit potential (E_OCP), polarization curves (PC) and electrochemical impedance spectroscopy (EIS). The results showed that the protective capacity of these polymeric systems on stainless steel, mainly with regard to pitting, depends on the nature of the anion dopant used during electro-synthesis of the PPy film. The best performance was seen with the dopants pTS and BS.     

Photoelectronic and transport properties of polypyrrole doped with a dianionic dye

Polypyrrole (PPy) doped with dodecylsulfate (DS) and an organic dye (indigo carmine, IC) was electrochemically prepared and characterized by Raman spectroscopy and X-ray diffraction (XRD). The photoelectrochemical properties of PPy-DS and PPy-DS-IC in contact with an electrolytic solution containing a redox couple were studied using the theories for the semiconductor ∣ electrolyte interface. Results indicate that the system containing IC presents a higher photocurrent density under polychromatic illumination and faster response time when compared with PPy-DS. This fact was assigned to the formation of molecular-scale paths in PPy-DS-IC. The IC molecules lying perpendicularly between PPy chains, as confirmed by the X-ray analysis, could facilitate the mass transport at the interface and increase the ordering degree to provide better electronic charge transfer in the bulk. Although the photoelectrochemical devices presented here do not present all the properties of inorganic-based devices, we discuss some strategies to enhance the photoelectrochemical properties and response time of conducting polymers used in these type of systems.     

重构钢渣的胶凝性分析

在炼钢转炉排渣的同时,将一定比例的电炉还原渣和煤渣加入到渣盘中,利用熔融钢渣的余热对钢渣的组成和结构进行在线重构。结果表明,重构处理明显降低了钢渣中的fCaO含量,改善了钢渣的易磨性和压蒸安定性,钢渣粉的28d活性指数提高了10%～20%。     

Corrosion protection of mild steel by polypyrrole phosphate composite coating

Electrodeposition of polypyrrole phosphate (PPy–P) on mild steel (ST₁₂) was achieved in oxalic acid medium using cyclic voltammetry (CV) technique. Adherent and homogeneous PPy–P films were obtained. The corrosion behavior of mild steel with phosphate (PPy–P) coatings in 3.5% NaCl solutions was investigated through potentiodynamic polarization technique, open circuit potential–time curves, and electrochemical impedance spectroscopy (EIS). Based on a physical model for the corrosion of mild steel composite, the Zview (II) software was applied to the EIS to estimate the parameters of the proposed equivalent circuit. It was found that the PPy–P coatings could provide much better protection than PPy. The effect of phosphate on the morphology and structure of the passive film was investigated by scanning electron microscopy and electron dispersion X-ray analysis (EDX). The results reveal that the PPy–P coated electrode provided a noticeable enhancement of protection against corrosion process.     

Characterisation and corrosion protection properties of polypyrrole electropolymerised onto aluminium in the presence of molybdate and nitrate

This paper describes the first attempts for the electrosynthesis of polypyrrole films containing molybdate onto aluminium electrodes. Electrogeneration was carried out in an alkaline solution in the presence of molybdate, nitrate and the monomer. The optimum concentrations for electropolymerisation were chosen in order to improve the corrosion protection of the substrate. The coatings were characterised by SEM/EDX and IR spectroscopy and the cyclic voltammetric response of the film is discussed. Pitting corrosion resistance was studied by means of open circuit potential and potentiodynamic measurements. The results presented below show that molybdate remains entrapped into the polymer matrix, providing greater resistance to breakdown of passivity in chloride media.     

Inhibition of corrosion of mild steel by homopolymer and bilayer coatings of polyaniline and polypyrrole

Homopolymers and bilayers of polyaniline (PAni) and polypyrrole (PPy) coatings have been electropolymerized on mild steel by potentiodynamic synthesis technique in aqueous oxalic acid solutions. Characterization of coatings was carried out by cyclic voltammetry. Corrosion behavior of the polymer coated mild steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test and electrochemical impedance spectroscopy (EIS) techniques in various aqueous corrosive solutions. Corrosion test results clearly showed that PPy and PAni/PPy bilayer coatings served as a stable host matrix on mild steel against corrosion. However, bilayers of PAni and PPy did not exhibit good combined properties of each polymer, unlike expected. PPy exhibited the best corrosion resistance among all coatings.     

Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application

Nano-thin polypyrrole (PPy) layers were coated on chemically modified ordered mesoporous carbon (m-CMK-3) by an in situ chemical polymerization. Structural and morphological characterizations of m-CMK-3/PPy composites were carried out using field emission scanning electron microscopy. Pseudo-capacitive behavior of the deposited PPy layers on m-CMK-3 was investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. As results of this study, the thin layer of PPy in the composite electrode was effective to obtain fully reversible and very fast Faradaic reaction. A maximum discharge capacity of 427 F g⁻¹ or 487 F g⁻¹ after correcting for weight percent of PPy phase at the current density of 5 mA cm⁻², could be achieved in a half-cell setup configuration for the m-CMK-3/PPy composites electrode, suggesting its potential application in electrode material for electrochemical capacitors.     

Characterisation and corrosion studies of steel electrodes covered by polypyrrole/phosphotungstate using Electrochemical Impedance Spectroscopy

Polypyrrole/PW₁₂O₄₀³⁻ hybrid material was electrosynthesised on carbon steel electrodes in acetonitrile medium. The coatings obtained were characterised by Electrochemical Impedance Spectroscopy (EIS). On free-standing polypyrrole films the electrical response was mainly due to ion–ion charge transfer resistance, with a value of 175 Ω cm². A value of 2 × 10⁻⁵ S/cm was determined for the hybrid material conductivity. A charge transfer resistance about 7000 Ω cm² was obtained due to steel/oxide interface. Corrosion tests showed an important improvement in the protection against corrosion when the carbon steel electrodes were coated by these polymeric films.     

Corrosion protection of 1Cr18Ni9Ti stainless steel by polypyrrole coatings in HCl aqueous solution

Electrically conducting polypyrrole (Ppy) coatings doped with sodium dodecylsulfate (SDS) have been deposited on 1Cr18Ni9Ti stainless steel by anodic polymerization from aqueous solutions of pyrrole and sodium dodecylsulfate. The corrosion behavior of Ppy coated steel was investigated in 0.3 M HCl aqueous solution at room temperature by a combination of electrochemical measurement techniques and scanning electron microscopy. The steel is in active state at the open circuit potential and suffers from pitting corrosion when the polarization potential is higher than 210 mV versus SCE. The Ppy coating can increase the corrosion potential of the steel by more than 600 mV versus SCE, and the pitting corrosion potential by more than 500 mV versus SCE. Fifty-day exposure experiments indicated that the Ppy coating shows high stability, and can inhibit effectively the corrosion of the steel.     

Effect of gas-timing technique on structure and optical properties of sputtered zinc oxide films

Zinc oxide thin films were prepared by the RF magnetron sputtering using a gas-timing technique whereby the flow of argon into the sputtering chamber was controlled by an on–off sequence. With this technique, polycrystalline ZnO thin films on glass substrates have been achieved without any thermal treatment of the substrate. In addition, the RF power and the gas-timing sequence can be fine-tuned to produce the hexagonal structure of ZnO thin films. X-ray diffraction (XRD) measurements confirm a (0 0 2) plane oriented wurtzite structure ZnO thin films. The optimized conditions for this hexagonal structure are an RF power of 30 W and an on–off gas-timing sequence of 50:2 s. The root mean square surface roughness of ZnO thin films measured by atomic force microscopy are in the range of 6.4–11.5 nm. The optical transmittance of ZnO thin films is over 85% in the visible range.     

Preparation of polypyrrole/ferrocyanide films modified carbon paste electrode and its application on the electrocatalytic determination of ascorbic acid

Functionalized polypyrrole film were prepared by incorporation of (Fe(CN)₆)⁴⁻ as doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrochemical behavior of the (Fe(CN)₆)³⁻/(Fe(CN)₆)⁴⁻ redox couple in polypyrrole was studied by cyclic voltammetry and double step potential chronoamperometry methods. In this study, an obvious surface redox reaction was observed and dependence of this reaction on the solution pH was illustrated. The electrocatalytic ability of polypyrrole/ferrocyanide films modified carbon paste electrode (Ppy/FCNMCPEs) was demonstrated by oxidation of ascorbic acid. It has been found that under optimum condition (pH 7.00), the oxidation of ascorbic acid at the surface of such electrode occurs at a potential about 540 mV less positive than unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α and catalytic reaction rate constant, k_h′, were also determined by using various electrochemical approaches.The catalytic oxidation peak current showed a linear dependent on the ascorbic acid concentration and a linear calibration curve was obtained in the range of 4.5×10⁻⁴ to 9.62×10⁻³ M of ascorbic acid with a correlation coefficient of 0.9999. The detection limit (2σ) was determined as 5.82×10⁻⁵ M.     

Voltammetric determination of ascorbic acid and dopamine in the same sample at the surface of a carbon paste electrode modified with polypyrrole/ferrocyanide films

Functionalized polypyrrole film were prepared by incorporation of [Fe(CN)₆]⁴⁻ as a doping anion, during the electropolymerization of pyrrole onto a carbon paste electrode in an aqueous solution by potentiostatic method. The electrochemical behavior of dopamine (DA) and ascorbic acid (AA) in one solution was studied at the surface of bare and modified carbon paste electrodes using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and differntial pulse voltammetry (DPV) methods. The well separated anodic peaks for oxidation of DA and AA were observed at the surface of the modified carbon paste electrode under optimum condition (pH 6.00), which can be used for determination of these species simultaneously in mixture by LSV and DPV methods. The linear analytical curves were obtained in the ranges of 0.10-1.00 mM and 0.10-0.95 mM for ascorbic acid and 0.10-1.20 mM and 0.20-0.95 mM for dopamine concentrations using LSV and DPV methods, respectively. The detection limits (2σ) were determined as 3.38 × 10⁻⁵ M and 1.34 × 10⁻⁵ M of ascorbic acid and 3.86 × 10⁻⁵ M and 1.51 × 10⁻⁵ M of dopamine by CV and DPV methods.     

EQCM study of polypyrrole modified electrodes doped with Keggin-type heteropolyanion for cation detection

The incorporation of a Keggin-type heteropolyanion, the phosphotungstate ([PW₁₂O₄₀]³⁻), into polypyrrole has been achieved during the electrochemical preparation of the polymer films in aqueous solution. The redox behaviour of these modified electrodes is described by using cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM). The data allowed to estimate the doping level that indicates the extent of the heteropolyanion insertion. It is found that the polymer films, in aqueous solution, exhibit sensibility to cations, namely to Na⁺.