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.     

Comparison of the corrosion protection of mild steel by polypyrrole–phosphate and polypyrrole–tungstenate coatings

The electrodeposition of polypyrrole–phosphate (PPy–P) and polypyrrole–tungstenate (PPy–W) on mild steel (MS) were achieved in an oxalic acid medium with cyclic voltammetry techniques. Adherent and homogeneous PPy–P and PPy–W films were obtained. The corrosion behavior of mild steel with phosphate (PPy–P) and tungstenate (PPy–W) composite coatings in 3.5% NaCl solutions were investigated through a potentiodynamic polarization technique, open‐circuit potential–time curves, and electrochemical impedance spectroscopy (EIS). On the basis of a physical model for corrosion of mild steel composites, Zview (II) software was applied to the EIS to estimate the parameters of the proposed equivalent circuit. It was found that the PPy–W coatings could provide much better protection than the PPy–P and polypyrrole coatings. The effects of the phosphate and tungstenate process parameters on the morphology and structure of the passive films were investigated by scanning electron microscopy and electron dispersion X‐ray analyses. The results reveal that the PPy–P and PPy–W coated electrodes offered a noticeable enhancement in protection against corrosion processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Simple and rapid synthesis of NiO/PPy thin films with improved electrochromic performance

Nickel oxide/polypyrrole (NiO/PPy) thin films were deposited by a two step process in which the NiO layer was electrodeposited potentiostatically from an aqueous solution of NiCl₂·6H₂O at pH 7.5 on fluorine doped tin oxide (FTO) coated conducting glass substrates, followed by the deposition of polypyrrole (PPy) thin films by chemical bath deposition (CBD) from pyrrole mixed with ammonium persulfate (APS). The NiO/PPy films were further characterized for their structural, optical, morphological and electrochromic properties. X-ray diffraction study indicates that the films composed of polycrystalline NiO and amorphous PPy. Infrared transmission spectrum reveals chemical bonding between NiO and PPy. Rectangular faceted grains were observed from scanning electron microscopy results. The electrochromic (EC) property of the film was studied using cyclic voltammogram (CV), chronoamperometry (CA) and optical modulation. The NiO/PPy presents superior EC properties than their individual counterparts. The coloration/bleaching kinetics (response time of few ms) and coloration efficiency (358 cm²/C) were found to be improved appreciably. The dramatic improvement in electrochemical stability (from about 500 c/b cycles for PPy to 10,000 c/b cycles for NiO/PPy) was observed. This work therefore demonstrates a cost-effective and simple way of depositing highly efficient, faster and stable NiO/PPy electrodes for EC devices.     

Improvement of polypyrrole films for corrosion protection of zinc-coated AZ91D alloy

To improve the protection against the corrosion of AZ91D magnesium alloy provided by conducting polypyrrole (PPy) films, optimization of the electrochemical synthesis of the PPy film was investigated. The bi-layered PPy film was prepared under constant current control, first in a sodium tartrate solution containing molybdate and second in a sodium dodecylsulfate (DS) solution (after the AZ91D alloy was covered by zinc electroplating). Corrosion testing of the zinc-coated AZ91D alloy covered with the PPy film was performed in 3.5% NaCl solution. The more protective PPy film doped with tartrate ions (PPy-Tart film) was formed by the lower current density (CD). Doping of molybdate ions (MoO₄²⁻) into the PPy-Tart film significantly improved its corrosion protection properties. When the PPy-Tart-MoO₄ layer was covered by an outer PPy layer doped with DS ions, the corrosion protection was further improved. The imposition of ultrasonic waves during the electropolymerization of the inner PPy-Tart-MoO₄ layer was effective in the improvement of corrosion protection. The bi-layered PPy-Tart-MoO₄/PPy-DS film prepared under ultrasonic irradiation maintained the zinc-coated AZ91D alloy in the passive state during the corrosion test in NaCl solution for 221 h, during which no corrosion products appeared.     

Undoped polyaniline–surfactant complex for corrosion prevention

Due to the strict regulations on the usage of heavy metals as the additives in the coating industries, the search for effective organic corrosion inhibitors in replacement of metal additives has become essential. Electrically conducting polymers have been shown to be effective for corrosion prevention, but the poor solubility of these intractable polymers has been a problem. We have explored a polyaniline–4-dodecylphenol complex (PANi–DDPh) to improve the dissolution, and it has been shown to be an effective organic corrosion inhibitor. With the surfactant, DDPh, PANi could be diluted into the coatings, and the properties of the coatings were affected. An emeraldine base (EB) form of PANi was also found to be oxidized by the hardener. The oxidized form of polyaniline provides improved corrosion protection of metals than that of emeraldine base since the value of the standard electrode potential for the oxidized form of PANi is higher than that of EB. Additionally, the surfactant improves the wet adhesion property between the coating and the metal surface. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2849–2856, 1999     

Protective properties of PPy‐Au nanocomposite coatings prepared by sonoelectrochemisty and optimized by the Taguchi method

The polypyrrole (PPy) and polypyrrole‐Au (PPy‐Au) nanocomposite films have been sonoelectrochemically synthesized on St‐12 steel electrodes using the galvanostatic technique. Experimental design according to the Taguchi method has been applied to optimize the factors on the synthesis of PPy‐Au nanocomposite coating. Three factors were used to design an orthogonal array L9: Synthesis time (t), Current density (I), and Concentration of HAuCl₄ (C). The synthesized Au nanoparticles during polymerization were characterized by Ultraviolet–visible (UV‐visible) spectroscopy. Characterization of the surfaces was done by scanning electron microscope (SEM), energy dispersive X‐ray spectrum (EDX), and atomic force microscope (AFM). The scanning electron microscopy (SEM) image of PPy shows a smooth surface while PPy‐Au nanocomposite film has a compact morphology. Moreover, energy dispersive X‐ray spectrum (EDX) is evidence for the incorporation of Au nanoparticles. The corrosion protection of coatings was investigated by open circuit potential (OCP) time trends, potentiodynamic polarization technique, and electrochemical impedance spectroscopy (EIS) in a NaCl 3.5% solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41087.     

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.     

Electrochemical behaviour of PANi/polyurethane antifouling coating in salt water studied by electrochemical impedance spectroscopy

Electrochemical behaviour of polyaniline–polyurethane (PANi–PU) antifouling coating in 3.5 wt% NaCl is studied by electrochemical impedance spectroscopy (EIS). A thick coating (∼1 mm) of 10, 15 and 20% PANi in marine grade PU, is cast over corrosion resistant aluminium alloy 2024 and its impedance characteristics are measured by EIS and compared with neat PU. On addition of 10% PANi, the impedance of the coating drastically comes down from 10⁹ to 10⁷ Ω. 20% is the maximum processable amount of PANi for the selected PU system. The coatings are exposed to 3.5 wt% NaCl and its impedance characteristics are monitored as a function of time. Changes in the impedance characteristics of the systems were found to occur as a function of the exposure time in all cases, though their evolution with time showed marked differences with PANi content. Water sorption and break down frequency are derived from the experimental results and analysed.     

聚苯胺在金属防腐领域中的应用

聚苯胺是最有应用价值的导电高分子之一,综述了聚苯胺在金属防腐领域的最新应用,讨论了其相关的防腐机理,并对PAN i的未来进行了展望。聚苯胺的存在使得金属和聚苯胺膜界面处形成一层致密的金属氧化膜,使该金属的电极电位处于钝化区,而使金属得到保护。聚苯胺作为防腐涂层具有独特的抗划伤和抗点蚀性能,是一种具有广阔前景的并适合于严酷条件下的新型金属腐蚀涂料。     

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.     

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.     

Electrochemical synthesis of polypyrrole (PPy) and PPyǀmetal composites on copper electrode and investigation of their anticorrosive properties

This study reports corrosion protection behaviour of various metal cations electrodeposited onto polypyrrole (PPy) coated copper (Cu) electrode. Before electropolymerization of pyrrole, the Cu electrode was passivated in 0.1 M oxalic acid via cyclic voltammetry method. After the coating process, metal cation electrodeposition onto PPy coating was carried out in 10⁻² M CuCl₂, ZnCl₂, FeCl₂ and NiCl₂ solutions. Corrosion behaviour of uncoated, PPy and PPy|metal coated Cu electrodes was studied in 0.1 M H₂SO₄ solution by using potentiodynamic polarization, chronoamperometric and impedance spectroscopic measurements. Surface morphologies were examined by scanning electron microscope (SEM). All the electrochemical measurements were in good agreement showing that metal electrodeposited PPy coated Cu electrodes have a higher corrosion resistance. Furthermore, SEM results show that while all the samples have a homogeneous distribution of metal cations, zinc and nickel have a much better homogeneous distribution compared to copper and iron. It was found that the best corrosion protection is provided by PPy|Zn and PPy|Ni coatings and there is a significant increase in their polarization resistance with increasing amounts of electrodeposited cations.     

Corrosion inhibition by poly(N-ethylaniline) coatings of mild steel in aqueous acidic solutions

Poly(N-ethylaniline) (PNEA) coatings on mild steel have been electrodeposited from 0.1 to 0.5 M aqueous oxalic acid solutions containing 0.1 M N-ethylaniline (NEA) using potentiodynamic synthesis technique. The effect of oxalic acid concentration on the corrosion behavior of PNEA coated mild steel surfaces were investigated by DC polarization and electrochemical impedance spectroscopy (EIS) techniques in 0.1 M HCl and 0.05 M H₂SO₄ solutions. Corrosion test results showed that corrosion resistance of PNEA coatings decreases with increasing concentrations of oxalic acid in polymerization solution. Decreasing acidity of the polymerization solution causes more effective protection against corrosion in aqueous acidic corrosive medium.     

Nanostructured coatings approach for corrosion protection

Nanostructured surface treatment coatings based on the Self-assembled Nanophase Particle (SNAP) approach were investigated as potential replacement for chromate-based surface treatments on aircraft aluminum alloys. In the traditional sol–gel method, hydrolysis-condensation processes are followed by condensation polymerization upon film application. This process sequence provides a low temperature route to the preparation if thin coatings which are readily applied to most metallic substrates. The recent discovery of a method of forming functionalized silica nanoparticles in situ in an aqueous sol–gel process, and then cross-linking the nanoparticles to form a thin film, is an excellent example of a nanoscience approach to coatings. This Self-assembled Nanophase Particle (SNAP) process can be used to form thin, dense protective organic surface treatment coatings on Al aerospace alloys. The ability to design coating components from the molecular level upward offers tremendous potential for creating multifunctional coatings.

The important components of Al alloy corrosion inhibition by chromate are storage and release of Cr^VI species, inhibition of cathodic reactions (primarily oxygen reduction), and inhibition of attack at active sites in the alloy. Unlike chromate-based treatments, current SNAP coatings provide barrier-type corrosion resistance but do not have the ability to leach corrosion inhibitors upon coating damage and minimize corrosion of the unprotected area. In this study, organic inhibitors were tested for corrosion protection of aluminum alloys in combination with the (SNAP). Scanning Vibrating Electrode Technique, anodic polarization, electrochemical impedance spectroscopy, and salt spray test were used to study this new approach for chromate replacement.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

Hierarchical polymer nanocomposite coating material for 316L SS implants: Surface and electrochemical aspects of PPy/f-CNTs coatings

Biocompatible nanocomposite coatings can be synthesized to offer improved surface properties for biomaterials and biomedical implants. Nanocomposite coatings containing polypyrrole (PPy) matrix reinforced with functionalized multi-wall carbon nanotubes (f-CNTs) were deposited on 316L SS substrates using electrochemical route. FT-IR, XRD, SEM, and TEM were employed to characterize the nanocomposite microstructure. High resolution imaging showed relatively uniform dispersion of the CNTs in the nanocomposite with a typical tubular structure. Micro-indentation tests revealed improvement in the hardness of the PPy/CNTs coatings. Measurement of the contact angle indicated enhanced surface wettability of the nanocomposite coatings. The corrosion behavior of 316L SS samples coated with PPy/CNTs was studied in SBF medium. The corrosion potential and the breakdown potential of coated 316L SS substrates shifted to more noble values as compared to uncoated 316L SS samples. The results suggest that incorporating CNTs as reinforcements in PPy coatings can provide enhanced properties in terms of surface hardness, biocompatibility, and 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.     

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.     

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.     

改性聚吡咯材料去除水中氟离子的性能

通过控制合成条件和在聚合过程中分别引入酸性红G（ARG）、甲基橙（MO）、α-环糊精（α-CD）和甲基橙等掺杂剂合成了表面带有毛刺的纤维、不同直径纳米纤维编织成的微米片状特殊微形貌的改性聚吡咯（PPy）材料。通过场发射扫描电子显微镜（SEM）、透射电子显微镜（TEM）、傅里叶变换红外光谱分析（FTIR）、氮气吸脱附分析（BET）、zeta电位分析等方法对其物理化学性能进行了表征,并将其应用于水体低浓度氟离子的吸附去除,比较了改性聚吡咯材料与传统方法合成的颗粒状聚吡咯对氟离子吸附的性能。结果表明：改性的特殊微形貌PPy的比表面积比传统颗粒状PPy提高了7~10倍;在常温和pH=5的条件下,F^-初始浓度在3~5mg/L,投加量为2g/L时,改性的特殊微形貌PPy可在10min之内达到吸附平衡,并将F^-的浓度降低到国家《生活引用水卫生标准》（GB 5749—2006）规定的1mg/L以下,说明特殊微形貌的控制对PPy吸附F^-具有很大影响。另外,该吸附行为是自发的放热过程,Langmiur模型可以很好地拟合该吸附过程,PPy对F^-的去除主要涉及离子交换作用。