Sweet aqueous solution for electrochemical synthesis of polypyrrole: Part 2. On ferrous metals

The electrochemical synthesis of polypyrrole on iron has been fruitfully achieved in aqueous medium of sodium saccharinate and pyrrole. The obtained coating under these conditions has been reached with cyclic voltammetry and chronomethods. The applied current density has a great effect on the thickness of PPy electrodeposited on iron electrodes. The characterization techniques show a good homogeneity of the PPy coating. The corrosion behaviour of PPy/Fe was investigated in sodium chloride by linear polarization, electrochemical impedance spectroscopy, and weight loss. The results show that PPy coating electrodeposited could provide a good protection against corrosion.     

Poly(N-methylpyrrole) electrodeposited on copper: Corrosion protection properties

Electrochemical synthesis of poly(N-methylpyrrole) films on copper electrodes from an aqueous oxalic acid has been achieved. A potential higher than 2 V (SCE) was needed to generate the polymer, for this reason, the polymer was in the overoxidized state. The inhibiting corrosion properties of this coating on copper were investigated for the first time in aqueous 0.1 M sodium chloride solution using potentiodynamic polarization, Tafel analyses, open-circuit potential and electrochemical impedance spectroscopy. Corrosion protection properties comparable to those of polypyrrole (PPy) films were observed for these films. A physical barrier effect is the most likely protection mechanism.     

Electrodeposition of bilayered polypyrrole on 316 L stainless steel for corrosion prevention

The electropolymerization of pyrrole in aqueous solutions of salicylate leads to the formation of hollow rectangular-sectioned microtubes. With the aim to develop a coating with this morphology but with better anticorrosive properties we synthesized a bilayer system by depositing a polypyrrole underlayer electropolymerized in the presence of molybdate and nitrate and a polypyrrole film formed by the microtubes as a top layer. The corrosion performance of the coatings was monitored by following the open circuit potentials, polarization curves and electrochemical impedance spectroscopy in acid and neutral chloride solutions. The bilayers have the capacity to protect the steel against uniform as well as against pitting corrosion during long exposure times. The system with the inner layer formed in alkaline solution was the most protective coating in this study. The results are discussed in terms of the galvanic interaction between the polymer and the substrate and the role played by the dopant anions.     

The use of polyindole for mild steel protection

Synthesis of polyindole was achieved on mild steel electrode previously coated with a very thin polypyrrole layer (PPy). Cyclic voltammetry technique was used for both syntheses; oxalic acid solution was used for synthesis of primer PPy coating and polyindole film (PI) was obtained from LiClO₄ containing acetonitrile medium. The corrosion performance of this PPy/PI coating was investigated properly in 3.5% NaCl solution by using anodic polarization and open circuit potential (E_ocp)–time curves and electrochemical impedance spectroscopy (EIS). This coating exhibited excellent barrier efficiency for a long time (about 190 h) and it was also able to provide a certain anodic protection. After 240 h of immersion time in corrosive test solution, the protection efficiency value was determined to be 98.9%.     

Effect of saccharin addition on the corrosion resistance of polypyrrole coatings

Electropolymerization baths for polypyrrole coating typically consist of two main constituents: monomer and counter-ion. By adding saccharin as the third constituent, a new branch emerges in electropolymerization that will yield coatings with modified properties. In the present study, polypyrrole is galvanostatically deposited onto carbon steel in an aqueous solution containing 0.2 M pyrrole and 0.1 M oxalic acid as the supporting electrolyte with (0.25, 0.5, 2.5 g/l) and without saccharin addition. Determination of the corrosion resistance of coatings in 0.1 M NaCl solution shows that in the presence of 0.5 g/l saccharin, a more noble corrosion potential and a greater corrosion resistance are obtained. Electrochemical impedance spectroscopy (EIS) revealed that the corrosion process was under infinite diffusion control of ions during prolonged immersion. The results indicate that the lower diffusion rate of ions in the coating produced in the presence of 0.5 g/l saccharin is responsible for its better corrosion resistance. Atomic force microscopy (AFM) shows that greater compaction of the coating produced in the presence of 0.5 g/l saccharin could be the reason for its higher corrosion resistance.     

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.     

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.     

Electrochemical synthesis of bilayer coatings of poly(N-methylaniline) and polypyrrole on mild steel and their corrosion protection performances

Homopolymer and bilayer coatings of poly(N-methylaniline) (PNMA) and polypyrrole-dodecylsulfate (PPy-DS) have been electropolymerized on a mild steel (MS) surface by the potentiodynamic method in aqueous oxalic acid solutions. In order to include dodecylsulfate ion as dopant in the polypyrrole, sodium dodecylsulfate was also added to the polymerization solution of pyrrole. Characterization of coatings was carried out by the cyclic voltammetry, Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM). Corrosion behavior of the polymer coated MS electrodes was investigated in highly aggressive 0.5 M HCl solution by the Tafel test and electrochemical impedance spectroscopy (EIS) techniques. Corrosion test revealed that among the protective coatings obtained, the PNMA/PPy-DS bilayer exhibited the best corrosion resistance at all immersion times.     

Sweet aqueous solution for electrochemical synthesis of polypyrrole part 1B: On copper and its alloys

The electrochemical synthesis of polypyrrole (PPy) on copper and brass has been successfully achieved in sodium saccharinate and pyrrole aqueous medium. The synthesized coating under several electrochemical techniques such as cyclic voltammetry, galvanostatic and potentiostatic is homogeneous and adherent. PPy has been characterized by SEM, XPS, IR and Raman spectroscopy and its quality has been confirmed. The doping level obtained from N 1s XPS signal of the oxidized PPy depends on the electrochemical technique used to produce the film. The corrosion performance of PPy/copper and PPy/brass has been evaluated in 3% NaCl and 0.1 M HCl using linear polarization and electrochemical impedance spectroscopy. The results show that PPy coating electrodeposited from sodium saccharinate exhibits significant corrosion protection properties.     

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.     

Investigations on the corrosion of copper patterns in the course of the “post-CMP cleaning” of integrated electronic microcircuits in oxalic acid aqueous solutions

An unknown corrosion process producing dendrites was recently found to take place at copper patterns immersed in oxalic acid aqueous solutions in the course of the post-chemical-mechanical polishing of integrated microcircuits (ICs). We report here investigations of this corrosion phenomenon in ICs using atomic force microscopy (AFM), cyclic voltammetry and Raman spectroscopy. AFM first allowed an accurate morphological characterisation of the copper patterns and their surroundings while cyclic voltammetry was used to identify their electrochemical reactivity in oxalic acid aqueous solutions. In situ AFM experiments carried out in this same aqueous media in open circuit conditions unambiguously showed a progressive and partial dissolution of copper patterns as well as the formation of a ring type structure. Raman spectroscopy was used on gold supported electrogenerated copper films to identify the precipitation or adsorption products resulting from the electrochemistry of the copper/oxalic acid system as a function of the applied potential and the pH of the oxalic acid aqueous solutions. The collected results rather suggest a two-step galvanic corrosion phenomenon involving the tantalum barrier, copper seed layer and electrodeposited copper.     

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.     

Influence of electrochemically prepared poly(pyrrole-co-N-methyl pyrrole) and poly(pyrrole)/poly(N-methyl pyrrole) composites on corrosion behavior of copper in acidic medium

Poly(pyrrole-co-N-methyl pyrrole) copolymer and poly(pyrrole)/poly(N-methyl pyrrole) bilayer composites were electrochemically synthesized on copper by cyclic voltammetry from aqueous solution of 0.3 M oxalic acid and 0.1 M monomer. Synthesis of copolymers were performed with different monomer feed ratios (pyrrole:N-methyl pyrrole, 8:2, 6:4, 5:5, 4:6 and 2:8) and in order to determine the copolymer, which has the best corrosion performance, anodic polarization was applied to copolymer coated samples. It was found that the performance of coatings was strongly dependent to the monomer feed ratio and the copolymer synthesized with 8:2 concentration ratio showed the most protective property compared to others. Bilayer of poly(pyrrole)/poly(N-methyl pyrrole) was also synthesized to compare the anticorrosive properties. Polymer films were characterized by ATR-FTIR spectroscopy and SEM techniques. Corrosion behavior of polymer composites was investigated in 0.1 M H₂SO₄ solution by anodic polarization and electrochemical impedance spectroscopy. Different approaches such as phase angle at high frequency and areas under Bode plots were used to evaluate corrosion performances of the coatings. Copolymer and bilayer coatings were found to have higher protection effect than single polypyrrole coatings. Moreover, bilayer coating exhibited better protection efficiency than copolymer coating against corrosion of copper when the obtained results were compared.     

Investigation of corrosion performance of epoxy coating containing polyaniline nanoparticles

An emulsion polymerization of aniline was performed in a solution of dodecylbenzenesulfonic acid emulsifier, benzoyl peroxide oxidant and tartaric acid as dopant. The polyaniline-containing coating was applied over carbon steel panels and the polyaniline content in the coating was 1?%. The influence of reactants concentration on the morphological and anti-corrosive properties of polyaniline was investigated to determine the optimum conditions for the synthesis of polyaniline nanoparticles. The average size of particles determined by X-ray diffraction measurement was 70?C104?nm, which is found to be in agreement with the scanning electron microscopy results. Corrosion resistance of coatings was obtained using electrochemical techniques (electrochemical impedance spectroscopy and open circuit potential measurements) in 3.5?% sodium chloride solution. Nyquist diagrams showed two capacitance loops, one at high frequency range followed by a larger one at low frequencies due to coating and charge transfer resistance. The corrosion resistance values were found to decrease due to the corrosion of carbon steel in pinholes of the coating. For longer immersion times, the coating resistance values were found to increase due to the passivation effect of polyaniline. The results showed that epoxy coating with doped polyaniline nanoparticles is able to offer protection in sodium chloride solution.     

Polypyrrole electropolymerized on aluminum alloy 1100 doped with oxalate and tungstate anions

Polypyrrole films doped with oxalic acid and tungstate were potentiostatically electropolymerized on aluminum alloy 1100. Two statistical factorial designs (fractional and complete) were used to study the influence of the synthesis variables on the film performance against corrosion. Corrosion protection of the polypyrrole films doped with oxalate and tungstate anions (PPy/OXA/W) on the aluminum alloy was evaluated by potentiometric and electrochemical impedance spectroscopy (EIS) measurements in a 0.05 mol L⁻¹ NaCl solution. The results obtained showed that the best performance against corrosion was detected with the PPy/OXA/W film synthesized at 1.0 V, 1.5 C in 0.2 mol L⁻¹ pyrrole, 0.1 mol L⁻¹ oxalic acid and 0.05 mol L⁻¹ sodium tungstate solutions provide a protective effect against corrosion.     

Analysis of corrosion products beneath an epoxy-amine varnish film

In situ Raman analysis was applied to identify the corrosion products formed on iron coated with epoxy-amine varnish and exposed to sodium chloride solution saturated by hydrogen sulfide or carbon dioxide. The results showed the formation of iron sulfide or iron carbonate layer while electrochemical impedance spectrum predicted the polymer coating exhibiting an almost perfect protecting barrier property. It is concluded therefore, that the corrosion process involves the permeation of water and hydrogen sulfide at molecular state through polymer interstices whereas no ionic conduction is allowed to take place in the coating film. The corrosion process induces the complete delamination of the exposed coating area but as far as its integrity is respected (no macroscopic pores or crevices) the corrosion rate is very low, far from that expected from permeation measurements of H₂S.     

Sweet aqueous solution for electrochemical synthesis of polypyrrole: Part 1-A. On non-ferrous metals

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminum electrode in aqueous medium of 0.1 M saccharin sodium salt and 0.5 M pyrrole. Scanning electron microscopy shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. Moreover, energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) reveal a good homogeneity of the film achieved in cyclic voltammetry during 10 cycles. The electrochemical impedance spectroscopy (EIS) results show that the coating decreases the polarization resistance of the aluminum electrode. The open circuit potential (OCP) and dc polarization measurements achieved in HCl and NaCl solutions displayed a large positive displacement of corrosion potential and a reduction of corrosion current in the case of PPy coating electrode in comparison with electrode bare.     

酸性化学镀Ni-Zn-P工艺的研究

研究了硫酸锌、添加剂和pH值对镀层沉积速率及镀层腐蚀电位的影响.测试了镀层在质量分数为3.5%的NaCl溶液中的Tafel曲线;用电化学阻抗实验对镀层的耐蚀性进行了测试.研究结果表明:镀层在质量分数为3.5%的NaCl溶液中,相对甘汞电极的腐蚀电势为-0.600 9 V,比化学镀Ni-P合金镀层的腐蚀电势-0.343 V低258 mV.     

Molybdate‐doped copolymer coatings for corrosion prevention of stainless steel

The polypyrrole and polyaniline copolymer coating (PPy‐PAni) and PPy‐PAni doped with sodium molybdate copolymer coating ( ) were synthesized on stainless steel by cyclic voltammetry. The effect of molybdate on the passivation of stainless steel was investigated by linear sweep voltammetry in 0.2 mol L^?1 of oxalic acid. The corrosion prevention performances of these copolymer coatings for stainless steel were investigated by linear sweep voltammetry, electrochemical impedance spectroscopy in 1 mol L^?1 of sulfuric acid, and potentiodynamic polarization in 0.1 mol L^?1 of hydrochloric acid. Copolymer coating doped with molybdate could accelerate the formation of the passive oxide film and have better corrosion prevention efficiencies than PPy‐PAni coating on stainless steel. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40602.     

Synthesis and corrosion protection aspects of poly(<Emphasis Type="Italic">o</Emphasis>-toluidine)/CdO nanoparticle composite coatings on mild steel

This study examines the possibility of using poly(o-toluidine)/CdO (POT-CdO) nanoparticle composite coating for corrosion protection of mild steel in chloride environment. The POT-CdO nanoparticle composite coating was synthesized on mild steel from aqueous tartrate solution containing CdO-nanoparticles (size ~18 nm) by using cyclic voltammetry. These coatings were characterized by cyclic voltammetry, UV–Visible absorption spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction measurements. The corrosion protection aspects of the resulting POT-CdO nanocomposite structure were investigated in aqueous 3% NaCl solution by potentiodynamic polarization technique and electrochemical impedance spectroscopy. The results of these investigations reveal that the POT-CdO nanoparticle composite acts as a protective coating on mild steel and reduces the corrosion rate of mild steel almost by factor of 70.