Electrochemical synthesis of poly-2-aminothiazole on mild steel and its corrosion inhibition performance

2-Aminothiazole (AT) was polymerized by electrochemical technique on a mild steel (MS) electrode from 0.01 M monomer containing 0.3 M ammonium oxalate solution. Cyclic voltammetry was used for the synthesis. Poly-2-aminothiazole (pAT) film with a light-brownish color was obtained on the MS surface. The effectiveness of polymer film in preventing corrosion of MS was tested in 0.5 M HCl solution. For corrosion tests, anodic polarization curves, electrochemical impedance spectroscopy (EIS) and linear polarization resistance (LPR) techniques were utilized. The results obtained indicated that, the polymer film adherent to the steel surface. The polymer film gives a good corrosion protection against the attack of corrosive environment.     

Electrochemical synthesis and characterization of poly-2-aminothiazole

2-Aminothiazole (2AT) was electrochemically polymerized on a Pt electrode using cyclic voltammetry (CV) technique from 0.01 M monomer containing 0.3 M ammonium oxalate solution. The high quality poly-2-aminothiazole (pAT) films with a light-brownish color were obtained on the Pt surface. The electrochemical behavior of the pAT-coated Pt electrode (Pt/pAT) was investigated in monomer-free 0.3 M ammonium oxalate solution by CV technique. The chemical structure characterization was investigated by UV–vis spectroscopy (UV–vis) and Fourier transform infrared spectroscopy (FTIR) techniques. The surface morphology of the polymer film was examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface morphology studies showed that, a homogeneous and compact film was formed on the Pt surface. Further, thermogravimetric analysis (TGA), differential thermal analysis (DTA) and differential scanning calorimetry (DSC) techniques were used to investigate the thermal properties of the polymer film. It was found that the thermal stability of the pAT film is relatively high. The solubility of the pAT was tested in common organic solvents as well as in acidic and basic solutions.     

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.     

Corrosion resistant behaviour of PANI–metal bilayer coatings

The present work discusses on the corrosion resistant behaviour of polymer metal bilayer coatings, viz. polyaniline (PANI), polyaniline–nickel (PANI–Ni), nickel–polyaniline (Ni–PANI), polyaniline–zinc (PANI–Zn) and zinc–polyaniline (Zn–PANI). The coatings were synthesized by means of cyclic voltametric method. The coatings thus obtained were uniform in nature and highly adherent to the mild steel substrate. The effectiveness of the coatings in preventing corrosion was tested by electrochemical impedance studies (EIS) using Nyquist and Bode plots and potentiodynamic polarization studies as well. Among the various coatings synthesized, the PANI–Zn coating was found to offer the maximum protection, followed by PANI–Ni coatings. Metal–PANI coatings were found to offer the least resistance to corrosion. The coatings thus obtained were characterized by scanning electron microscopic (SEM) analysis and the results are discussed.     

Polyaniline Top Coat Modified on Nickel-Plated Mild Steel: AC Impedance Analyzer

Polyaniline (PANI) was synthesized from 0.1 M aniline containing neutral medium such as sodium oxalate. The synthesis was achieved on 1-µm Ni-plated mild steel (MS/Ni) by using cyclic voltammetry technique. The corrosion performances of PANI coating with and without MS/Ni electrodes were evaluated by using AC impedance spectroscopy (EIS) and anodic polarization curves in 3.5% NaCl solution. It was found that Ni plating showed an important barrier property on MS. This case decreased drastically in longer periods, and the porosity values increased in chloride ions medium, which has small ion diameter. In the presence of PANI top coat, the porosity values remained almost constant against the attack of corrosive products for extended periods. It indicated that PANI coating could provide a significant protection property to MS/Ni, by catalyzing the formation of a stable nickel oxide layers with time. The catalytic behavior of polymer film also contributed to improvement of barrier property of PANI coating due to transformation to the reduced structure.     

Inhibition of nickel coated mild steel corrosion by electrosynthesized polyaniline coatings

Polyaniline (PANI) coatings were electrochemically synthesized on nickel (Ni) coated mild steel (MS) and their corrosion protection properties were investigated. In this work, the Ni layer (∼1 μm thick) was electrodeposited on MS under galvanostatic condition. Thereafter, the PANI coating was deposited over the Ni layer from aqueous salicylate medium by using cyclic voltammetry. These bi-layered composite coatings were characterized by cyclic voltammetry, UV–vis absorption spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The corrosion protection properties of Ni coated MS (Ni/MS) and PANI coated Ni/MS (PANI/Ni/MS) were investigated in aqueous 3% NaCl by using open circuit potential (OCP) measurements, potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). It was shown that the top layer of PANI exhibits a lower porosity behavior with respect to Ni coating and reduces the corrosion rate of Ni/MS almost by a factor of 3500 and increases the lifetime of Ni coating.     

Development of novel waterborne poly(1-naphthylamine)/poly(vinylalcohol)–resorcinol formaldehyde-cured corrosion resistant composite coatings

Advancements in the field of corrosion protective coatings have headed towards the utilization of conducting polymer-based blends and composites for the formulation of corrosive protective paints and coatings. With the aim to develop an ecofriendly waterborne conducting polymer-based protective coating material, corrosion protective behavior of waterborne resorcinol formaldehyde (RF)-cured composite coatings of poly(1-naphthylamine) (PNA)/poly(vinylalcohol) (PVA) was investigated on mild steel (MS). The corrosion protective performance was evaluated by physicochemical, physicomechanical, corrosion protective efficiency and resistance in acid, alkaline and saline media by open circuit potential (OCP) measurements. The morphologies of coated, uncoated as well as corroded samples were analyzed by SEM technique. Superior corrosion protective performance was observed which was compared to the reported solvent-based conductive polymer coatings in different corrosive media.     

Electrochemical synthesis and corrosion performance of poly(pyrrole-co-o-anisidine)

The electrochemical synthesis of poly(o-anisidine) homopolymer and its copolymerization with pyrrole have been investigated on mild steel. The copolymer films have been synthesized from aqueous oxalic acid solutions containing different ratios of monomer concentrations: pyrrole:o-anisidine, 9:1, 8:2, 6:4, 1:1. The characterization of polymer films were achieved with FT-IR, UV–visible spectroscopy and cyclic voltammetry techniques. The electrochemical synthesis of homogeneous-stable poly(o-anisidine) film with desired thickness was very difficult on steel surface. Therefore its copolymer with pyrrole has been studied to obtain a polymer film, which could be synthesized easily and posses the good physical–chemical properties of anisidine. The kinetics and rate of copolymer film growth were strongly related to monomer feed ratio. The introduction of pyrrole unit into synthesis solution increased the rate of polymerization and the substrate surface became covered with polymer film soon, while this process required longer periods in single o-anisidine containing solution. The protective behavior of coatings has been investigated against steel corrosion in 3.5% NaCl solution. For this aim electrochemical impedance spectroscopy (EIS) and anodic polarization curves were utilized. The synthesized poly(o-anisidine) coating exhibited significant protection efficiency against mild steel corrosion. It was shown that 6:4 ratio of pyrrole and anisidine solution gave the most stable and corrosion protective copolymer coating.     

Preparation and corrosion assessment of electrodeposited Ni–SiC composite thin films

Ni–SiC composite thin films were successfully prepared via direct-current (DC) and ultrasonic pulse-current (UPC) deposition. The morphologies, mechanical properties, and corrosion properties of the films were investigated via atomic force microscopy, X-ray diffraction (XRD), Vickers hardness test, scanning electron microscope (SEM), cyclic polarization, and gravimetric analysis. The results show that the Ni–SiC composite thin films synthesized via UPC deposition possess a compact and exiguous surface morphology. The XRD results indicate that the average grain diameters of Ni and SiC in the UPC-deposited thin film are 63.6 and 38.5 nm, respectively. The maximum microhardness values for the DC- and UPC-deposited Ni–SiC composite thin films prepared are 871.7 and 924.3 HV, respectively. In the corrosion tests, the UPC-deposited films have a higher corrosion resistance than those prepared by DC deposition with the same SiC content.     

Electropolymerized bilayer coatings of polyaniline and poly(N-methylaniline) on mild steel and their corrosion protection performance

Polyaniline (PANI) and poly(N-methylaniline) (PNMA) have been electrodeposited on mild steel from oxalic acid bath using cyclic voltammetric technique. Pretreatments like passivation and primer polymer coatings were required for effective coating. Differently stacked composite polymer layers on the metal surface by layer-by-layer approach have also been obtained and their properties have been compared with their corresponding copolymer coatings. FTIR study confirms the formation of electroactive polymer compounds on mild steel. Evaluation of these coatings in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy reveals significant corrosion resistant behavior. Relatively higher corrosion protection is exhibited by copolymer coatings and composite-bilayer coatings than the corresponding homopolymer coatings. The composite metal–PANI–PNMA layer shows higher stability and better protection than the metal–PNMA–PANI layer.     

Conducting polymers for corrosion protection: What makes the difference between failure and success?

The potential of conducting polymer coatings for corrosion protection is a topic of current controversy. In general, the efficacy of conducting polymers very much depends on how they are applied and on the conditions of the corrosion experiment, i.e. depending on the exact conditions a conducting polymer may have excellent protection capability or may lead to a disastrously enhanced corrosive attack. A number of possible protection mechanisms are proposed. The most interesting corrosion protection mechanism that is currently discussed for conducting polymer-based coatings is the intelligent release of inhibitor anions. However, in many cases this does not work in the presence of larger defects. Based on scanning Kelvin probe studies of artificial defect initiated reduction and delamination of polypyrrole films in nitrogen (reduction) or air (reduction and delamination) atmospheres it will be shown in this paper that this is due to a switching from mixed anion release and cation incorporation during reduction of the conducting polymer to an exclusive cation incorporation for reduction over extended length scales. Although only results for polypyrrole are discussed here, for fundamental reasons this is postulated to be of general validity for all conducting redox polymers such as polypyrrole, polyaniline, and polythiophene. Hence, all coatings based on pure conducting polymer layers or pigments with macroscopic percolation networks will fail in the presence of larger defects, even though they may show excellent corrosion protection for smaller ones.     

High performance corrosion protective DGEBA/polypyrrole composite coatings

Conducting polymers (CP) have been envisaged as nontoxic substitutes for chromates in corrosion protective coatings owing to their environmental stability, excellent corrosion resistant performances and good adhesion to metal substrate. Recent advancements in the field of corrosion protective coatings have therefore headed towards the utilization of conducting polymers as “smart corrosion inhibitors” in the formulation of eco-friendly anti-corrosive coatings. With the aim to develop a facile method for the synthesis of anti corrosive coating material having superior corrosion protective properties, the present work reports the corrosion studies of polypyrrole/DGEBA composite coatings on mild steel (MS). The coatings were characterized by physicochemical as well as physicomechanical studies while the corrosion protective performance was evaluated by chemical resistance in different corrosive media, corrosion rate and open circuit potential (OCP) measurements. The morphologies of corroded, coated, uncorroded and uncoated samples were investigated by SEM studies. The composite coatings were found to show far superior anti corrosive performance than PANI/epoxy coatings in acid, alkaline as well as saline environments.     

Poly(o-anisidine) on brass: Synthesis and corrosion behavior

The electrochemical synthesis of poly(o-anisidine) (POA) was achieved on brass (CuZn) electrode by applying two scan rates (50 and 20 mVs⁻¹). The synthesized polymer films were strongly adherent and homogeneous in both cases. Their corrosion performance was investigated by AC impedance spectroscopy (EIS) technique, anodic polarization plots and open circuit potential-time curves, in 3.5% NaCl solution. It was clearly seen that poly(o-anisidine) films provided a significant physical protection for longer exposure time. It was shown that polymer film coated at high scan rate (CuZn/POA-H) exhibited better barrier property against the attack of corrosive agents when compared with polymer film obtained at low scan rate (CuZn/POA-L). It was found out that poly(o-anisidine) film synthesized at high scan rate caused a significant increase in corrosion resistance by its catalytic behavior on formation of protective oxide layers on the surface in longer time.     

Polypyrrole films on nickel-plated copper

Polypyrrole (PPy) film was synthesized on nickel-plated copper electrodes, from monomer containing 0.2 M ammonium oxalate solution. The thickness of galvanostatically deposited nickel layer was 2 μm, while 0.80 μm thick polymer film was obtained by using cyclic voltammetry technique. The protective behavior of PPy modified nickel coating has been investigated, against copper corrosion in 3.5% NaCl solution. For this aim, ac impedance spectroscopy, the anodic polarization curves and open circuit potential–time (E_ocp–t) diagrams were utilized. It was shown that PPy modified nickel coating could provide important protection to copper for considerable periods, in such aggressive medium. The thin polymer film constituted a physical barrier on top of nickel layer against the attack of corrosive environment for a certain period. Also, it was found that the thin PPy film could increase the protection efficiency and lifetime of nickel coating, by its catalytic behavior on formation of NiO layer.     

Corrosion behavior of AISI 316 stainless steel coated with modified fluoropolymer in marine condition

In the maritime industry, stainless steel corrosion resistance requires further surface improvement and further enhanced protection using surface coatings. In this study, an engineered copolymer of polyvinylidene fluoride (PVDF) with polymethylmethacrylate (PMMA)-blended coating was found to provide outstanding corrosion resistance for metal surfaces affording protection against severely corrosive marine environments. Electrochemical measurements indicate that corrosion protection of 316 stainless steel was drastically increased when utilizing the KP blend (a combination of PVDF + PMMA), producing a new set of corrosion properties and morphological characteristics. The corrosion protection of the KP coating proved to be very effective in reducing the passive region current density from 2.19 × 10^?5 A/cm² (for bare stainless steel) to 2.63 × 10^?10 A/cm² and the breakdown passive region potential at 0.25 V. This was followed by a significant decrease in corrosion rate, when compared to pure PMMA and PVDF films, during exposure to artificial marine seawater. With the KP film, impedance measurements surpassed those of other films, with a noticeable nonpeak straight line in the phase angle diagram. Optical observation showed that corrosion pits and delamination areas existed under the coatings.     

Electrochemical impedance spectroscopy investigations of epoxy zinc rich coatings: Role of Zn content on corrosion protection mechanism

Effect of zinc content in the epoxy zinc rich coating on the mechanism of corrosion protection was investigated using electrochemical impedance spectroscopy (EIS). The zinc content in the coating (on dry film) was varied from 40% to 90% in steps of 10%. Open circuit potential (OCP) measurements and salt spray tests were also carried out to generate supporting evidences and to deepen the understanding in the area of zinc rich coatings. The healing or bridging ability of these coatings was studied by making a scribe on the coating and monitoring the evolution of OCP. EIS was also utilized to screen the amount of zinc particles required to provide efficient galvanic protection and to study the effect of purity of Zn on corrosion protection performance. Both EIS and OCP measurements indicate that coatings containing 40% Zn (on dry film) provides very good barrier protection coming mainly from polymer whereas the one containing >80% Zn provides excellent galvanic protection to the steel substrate. When the zinc loading is between 60% and 70%, coatings neither show barrier protection nor galvanic protection.     

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.     

Copper/polypyrrole multilayer coating for 7075 aluminum alloy protection

The corrosion behavior of 7075 aluminum (Al), copper modified Al (Al/Cu), polypyrrole modified Al (Al/PPy) and copper (under layer)/polypyrrole (top layer) modified Al (Al/Cu/PPy) samples were investigated in 3.5% NaCl solution. The copper plating on aluminum was carried out from acidic copper sulphate solution by electroless method. Polypyrrole (PPy) was electrochemically synthesized on Al and Al/Cu electrodes from 0.1 M pyrrole containing 0.4 M oxalic acid solution using cyclic voltammetry technique. The films synthesized were characterized by Fourier transform infrared spectroscopy (FT-IR). The thermal stability of PPy films was investigated by thermogravimetric analysis (TGA). The surface morphologies were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The corrosion behavior of samples was investigated by electrochemical impedance spectroscopy (EIS) and anodic polarization curves. The data obtained showed that the synthesis of PPy on top of the Cu layer significantly enhances the corrosion resistance of Al by exhibiting a barrier effect against the attack of corrosive environment.     

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.     

Wear-corrosion behavior of ultra-thin diamond-like carbon nitride films on aluminum alloy

Diamond-like carbon films exhibit high hardness, high wear resistance and a low friction coefficient. They are extensively utilized in the mechanical, electronic and biomedical industries. This work evaluates the effect of the thickness of ultra-thin diamond-like carbon nitride films on their corrosion properties and their wear-corrosion resistance in a mixed 1 M NaCl + 1 M H₂SO₄ solution using electrochemical methods. The corrosion current density and weight loss of all films during and after wear-corrosion test are also recorded. This work employs ion beam-assisted deposition (IBAD) to deposit DLC nitride films of various thicknesses (1.5, 2.0, 2.5 and 3.0 nm), containing 60% nitrogen gas in the form of a gaseous mixture of C₂H₂ + 60%N₂. The thickness of the films was measured using a transmission electron microscope (TEM). The atomic bonding structures of these DLC nitride films are analyzed using a Raman spectrometer and by electron spectroscopy for chemical analysis (ESCA). A scanning electron microscope (SEM) was adopted to elucidate the surface morphologies of the specimens after corrosion and wear-corrosion. The results indicated that all of the nitrogen-containing DLC films excellently protected the 5088 Al–Mg alloy substrate with an electroless plated Ni–P interlayer against corrosion, and that the degree of protection increases with the thickness of the film. In the wear-corrosion tests various potentials were applied during wear in the particular corrosive solution. The results further demonstrated that the wear-corrosion resistance of all the nitrogen-containing DLC films was as effective as corrosion protection, and that the wear-corrosion loss decreased as the film thickness increased.