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.     

Corrosion protection of steel by polyaniline blended coating

Phosphate doped polyaniline was synthesized from aqueous phosphoric acid containing aniline by chemical oxidation method using ammonium persulphate as oxidant. The polymer was characterized by UV–vis and FT-IR spectroscopic techniques. Using this polymer, a paint with 1% polyaniline was prepared with epoxy binder. The corrosion resistant property of the polymer containing coating on steel was found out by open circuit potential measurements and electrochemical impedance spectroscopic method in 0.1 N HCl, 0.1 N H₃PO₄ and 3% NaCl for a duration of 50 days. The coating was able to protect the steel more in 0.1 N H₃PO₄ and 3% NaCl media than in 0.1 N HCl.     

Corrosion inhibition of steel in sodium chloride solution by undoped polyaniline epoxy blend coating

In this study an undoped polyaniline (PAni) was synthesized by chemical oxidative polymerization with ammonium persulfate as an oxidizing reagent. The synthesized PAni was used as a corrosion inhibitive pigment in an epoxy matrix. The corrosion protection performance of steel coated panels in 3.5% sodium chloride solution was evaluated via determination of open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). It was found that after 300 days of immersing the resistance of coating was about 4 × 10⁵ Ω cm². The OCP was shifted to the noble region due to the passivation effect of PAni pigment. Besides, the phase angle (theta) at 10 kHz was stable around 87 ± 1° during immersion period. Results revealed that PAni pigmented paint showed acceptable protection against the corrosion of carbon steel in 3.5% sodium chloride solution.     

Optimization of electrochemical polymerization parameters of polypyrrole on Mg–Al alloy (AZ91D) electrodes and corrosion performance

We report on the optimum electropolymerization conditions of polypyrrole (PPy) coatings on Mg alloy AZ91D electrodes from aqueous electrolytes of sodium salicylate via cyclic voltammetry (CV). Results show that initial and end potential values during the electrochemical coating procedure play an important role on the adhesion and corrosion performance of PPy films. Corrosion tests of AZ91D electrodes coated with PPy under optimized conditions show a good corrosion performance during 10 days in Na₂SO_4, without peeling off of these thin films.     

Influence of pH on the synthesis and properties of polypyrrole on copper from phytic acid solution for corrosion protection

Polypyrrole (PPy) films were deposited on copper from “green” inhibitor of phytic acid solution for corrosion protection of copper. The corrosion protection property of the PPy layer was studied by an immersion test in a NaCl aqueous solution. The polymerization process of PPy on copper changed with the pH values of phytic acid solution and current density applied. When one oxidized bare copper in phytic acid solution at various pHs containing pyrrole monomer, a thin layer consisting of complex compound of Cu-phytate was firstly formed, followed by the formation of the PPy layer doped with phytate anion on the complex compound layer. The complex compound layer passivated the copper surface and its thickness increased with the lower pH value of the solution and the lower current density applied. It was found that the PPy coating prepared in the phytic acid solution at pH 4 exhibit the most protective property against copper corrosion.     

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.     

Corrosion inhibition of steel using mesoporous silica nanocontainers incorporated in the polypyrrole

Mesoporous silica nanocontainer powders were applied as corrosion inhibitor hosts. These powders were dispersed in the polypyrrole matrix by electropolymerization technique. The protection properties of these composite coatings with and without inhibitor were studied in 2 g dm⁻³ chloride ion solutions at constant pH. Open circuit potential (OCP), inductive coupled plasma (ICP), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and Fourier transform infrared spectroscopy (FTIR) results showed that the substrates were protected due to the release of corrosion inhibitor from mesoporous silica in the chloride media compared to the coatings without corrosion inhibitor. The released corrosion inhibitor reacted with substrate and made a protective phase during corrosion. This phase can heal the corroded area as a self-healing compound.     

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.     

Corrosion resistance properties of electroless nickel composite coatings

Electroless nickel (EN) composite coatings incorporated with PTFE and/or SiC particles demonstrated significantly improved mechanical and tribological properties as well as low surface energy which are desired for anti-sticking and wear resistant applications. The corrosion resistance of these composite coatings, however, has not been systematically studied and compared. This work aimed to investigate the corrosion characteristics of EN composite coatings using electrochemical measurements which include open circuit potential (OCP), electrochemical impedance spectroscopy and potentiodynamic test. The effects of the co-deposited particles on corrosion behavior of the coatings in 1.0 N H₂SO₄ and 3% NaCl media were investigated. The surface autocatalytic properties and the post-heat-treatment on coating corrosion resistance were also discussed. The results showed that both EN and EN composite coatings demonstrated significant improvement of corrosion resistance in both acidic and salty atmosphere. Ni striking substantially enhanced the corrosion resistance due to the improvement of the surface autocatalytic properties and homogeneity. Proper post-heat-treatment significantly improves the coating density and structure, giving rise to enhanced corrosion resistance.     

Electrochemical behavior and anticorrosion properties of modified polyaniline dispersed in polyvinylacetate coating on carbon steel

Conducting polyaniline (Pani) was prepared in the presence of methane sulfonic acid (MeSA) as dopant by chemical oxidative polymerization. The Pani-MeSA polymer was characterized by FT-IR, UV-vis, X-ray diffraction (XRD) and impedance spectroscopy. The polymer was dispersed in polyvinylacetate and coated on carbon steel samples by a dipping method. The electrochemical behavior and anticorrosion properties of the coating on carbon steel in 3% NaCl were investigated using open-circuit potential (OCP) versus time of exposure, and electrochemical techniques including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and cyclic voltammetry (CV). During initial exposure, the OCP dropped about 0.35 V and the interfacial resistance increased several times, indicating a certain reduction of the polymer and oxidation of the steel surface. Later the OCP shifted to the noble direction and remained at a stable value during the exposure up to 60 days. The EIS monitoring also revealed the initial change and later stabilization of the coating. The stable high OCP and low coating impedance suggest that the conducting polymer maintains its oxidative state and provides corrosion protection for carbon steel throughout the investigated period. The polarization curves and CV show that the conducting polymer coating induces a passive-like behavior and greatly reduces the corrosion of carbon steel.     

Electrochemical synthesis and redox behaviour of polypyrrole coatings on copper in salicylate aqueous solution

In this work, polypyrrole (PPy) coatings have been successfully electrodeposited on copper substrates from aqueous salicylate solutions. Homogenous and uniform films can be grown under galvanostatic or potentiostatic control without noticeable substrate dissolution. The redox behaviour obtained for the films is similar to that displayed by PPy grown under the same conditions on noble metals. Strong adherence to copper is observed as far as PPy is in its oxidised state but it is lost when the system is subjected to potentials lower than −0.5 V versus saturated calomel electrode (SCE).     

Modulation of the interfacial electrochemistry of surfactant-functionalised polypyrrole chemical sensor systems

The redox properties of electro-polymerized polypyrrole (Ppy) doped with different surfactants were studied in acid medium. It was found out that the addition of different surfactants affect the redox properties as evidenced by diffusion coefficients and rate constants calculated from experimental data obtained from cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Three different surfactants were incorporated into polypyrrole matrix to form homogeneous composites i.e. anionic surfactant polyvinylsulphonic acid (PVSA) as well as non-ionic surfactants (polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (Triton-X 100) and polyoxyethylene (20) sorbitan monolaurate (Tween 20). CV and EIS experiments were carried in the presence of the redox probe K₃[Fe(CN)₆]. Diffusion coefficient was interpreted as a measure of electron movement within the composite polymer structure and rate constant was interpreted as a measure of the rate of oxidation and reduction of the redox probe. The highest value for diffusion coefficient and rate constant was obtained for Ppy/PVSA as 8.16 × 10⁻¹² cm² s⁻¹ and 1.05 × 10⁻⁵ cm s⁻¹ respectively. The values obtained by CV and EIS were in good agreement.     

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.     

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.     

The electrochemical synthesis of polypyrrole at a copper electrode: corrosion protection properties

Pyrrole was successfully electropolymerized at a copper electrode in a near neutral sodium oxalate solution to generate a homogeneous and adherent polypyrrole film. The growth of these films was facilitated by the initial oxidation of the copper electrode in the oxalate solution to generate a copper oxalate pseudo-passive layer. This layer was sufficiently protective to inhibit further dissolution of the copper electrode and sufficiently conductive to enable the electropolymerization of pyrrole at the interface, and the generation of an adherent polypyrrole film. These films remained stable and conducting for periods exceeding eight days and exhibited significant corrosion protection properties in acidified and neutral 0.1 mol dm⁻³ NaCl solutions even on polarization to high anodic potentials.     

In situ atomic force microscopy investigation of copper behaviour and polypyrrole deposition from salicylate medium

The morphological modifications accompanying the electrochemical behaviour of copper in aqueous salicylate solution, have been investigated by in situ atomic force microscopy (AFM), with the purpose of elucidating the role of salicylate ions during polypyrrole electrodeposition onto this oxidisable metal.The surface changes revealed by in situ AFM images, are in agreement with previous attributed electrochemical processes, namely the formation of a non-uniform passivating layer, which does not completely block the copper surface. The presence of such layer prevents a strong anodic copper dissolution without hinder the pyrrrole oxidation. Pyrrole electropolymerization process has been also followed in real-time by AFM, and occurs through the formation of a first polymer layer, which follows the initial copper surfaces irregularities and is characterized by polypyrrole round nodules of different sizes, whereas for thick polymer films the influence of substrate defects is not detected.     

Corrosion resistance properties of Ormosil coatings on 2024-T3 aluminum alloy

The corrosion resistance behavior of organically modified silane (Ormosil) thin films on 2024-T3 aluminum alloy substrates was investigated using electrochemical impedance spectroscopy (EIS) and accelerated salt spray analysis techniques. Coatings were prepared containing 0–16.6 vol.% alkyl-modified silane, X_n---Si(OR)_4−n, where X=methyl, dimethyl, n-propyl, n-butyl, i-butyl, n-hexyl, n-octyl, or i-octyl. Coating thicknesses were measured to be in the 6–16 μm range, with the thickest coatings being observed for the highest concentrations of alkyl-modified silane. Contact angle measurements showed an enhancement in hydrophobicity of the Ormosil film imparted by increasing size and concentration of the alkyl-modifiers in the coating. In general, corrosion resistance characteristics, as determined using EIS and salt spray techniques, were found to increase with increasing alkyl-modified silane concentration and alkyl chain length. The best overall corrosion resistance was observed for coating systems containing ≥10.4 vol.% alkyl-modified silane; the hexyl-modified films exhibited corrosion resistance properties superior to the other Ormosil coatings. Immersion studies conducted in 0.5 M K₂SO₄ indicated that coating degradation occurs via hydration of the dense linear chain silicate network leading to the formation of porous cyclic structures.     

Anticorrosive properties of polypyrrole films modified with zinc onto SAE 4140 steel

Polypyrrole (PPy) films modified with zinc were electrosynthesized onto SAE 4140 steel in presence of bis(2-ethylhexyl) sulfosuccinate (AOT). The Zn and PPy electrodeposition was realized by using cyclic voltammetry at different temperatures. The corrosion protection properties of the films were examined in chloride solution by open circuit measurements, linear polarization and electrochemical impedance spectroscopy (EIS). The obtained results indicate that the presence of Zn in the polymer matrix improves the anticorrosive performance of PPy films. The best anticorrosion efficiency was obtained for the coatings modified at 20 °C which provided anodic protection to the steel substrate for a long period of immersion in chloride solution. Cathodic protection was observed when the electrodeposition temperature was increased. Adherence and anticorrosive properties declined sharply for the coatings electrosynthesized at 5 °C.     

Characterization and corrosion protection properties of polypyrrole / montmorillonite electropolymerized onto aluminium alloy 1100

Films of Polypyrrole/Montmorillonite (PPy/MT) clays were electropolymerized potentiostatically on aluminium alloy 1100, using sodium dodecylbenzenesulfonate (SDBS) as a dopant. Two clay species were used: Na⁺-Montmorillonite (MT-Na) and modified-Montmorillonite (MT-M). The characterization of the PPy/MT films performed by XRD and TEM shows that the exfoliation method employed, as well the electrochemical polymerization method used in this work, allow nanocomposite materials to be obtained. The PPy/MT films were found to have less electrical conductivity than pure PPy. The corrosion protection of aluminium alloy 1100 covering PPy/MT was evaluated by electrochemical techniques in 0.05 mol L⁻¹ NaCl medium. The electrochemical parameters derived from the polarization curves, together with the EIS data, revealed that the corrosion resistance of PPy/clay coatings depends on the type and concentration of Montmorillonite employed. The best performance in the corrosion protection of the aluminum was achieved with PPy/MT films containing 1% of clay.     

The corrosion protection of mild steel by single layered polypyrrole and multilayered polypyrrole/poly(5-amino-1-naphthol) coatings

Electrochemical synthesis of polypyrrole (PPy) and top coat of poly(5-amino-1-naphthol) (PANAP) on PPy films from oxalic acid solution was achieved on mild steel (MS) by cyclic voltammetry technique. The morphology and the structure of the films were investigated by scanning electron microscopy (SEM). The corrosion performance of this multilayer coating and single PPy coating were investigated in 3.5% NaCl solution by using open circuit potential (E_ocp)–time curves, polarization curves and electrochemical impedance spectroscopy (EIS). It was found that the multilayer PPy/PANAP coating could provide much better protection than single PPy coating for corrosion of MS. It was observed that corrosion performance of coatings was increasing with immersion period. This was explained by auto-undoping properties of PPy coatings during immersion in corrosive solution. The improved corrosion performance in the presence of PANAP top coat on PPy was explained by increase in barrier effect of bilayer films.