Corrosion protection coating containing polyaniline glass flake composite for steel

Corrosion protection of steel by glass flake (GF) containing coatings is widely used in marine atmosphere. Even though, the coatings containing glass flake are highly corrosion resistant, their performance is decreased due to the presence of pinholes and coating defects. It is well established that polyaniline containing coating is able to protect the pinhole defects in the coatings due to passivating ability of polyaniline. Hence a study has been made on the corrosion protection ability of steel using polyaniline-glass flake composite containing coating with 10% loading of glass flake in epoxy binder. The polyaniline glass flake composite (PGFC) was synthesized by chemical oxidation of aniline by ammonium persulphate in presence of glass flake. The corrosion protection ability of GF and PGFC containing coating on steel was found out by salt spray test and EIS test in 3% NaCl. In both the tests, the resistance value of the PGFC containing coating has remained at 10⁸-10⁹ Ω cm² where as for the GF containing coating, the resistance values decreased to 10⁵ Ω cm². The enhanced corrosion protection ability of the PGFC containing coating is due to the passivation ability of the polyaniline present in the coating.     

Polyaniline for corrosion prevention of mild steel coupled with copper

Polyaniline emeraldine base/epoxy resin (EB/ER) coating was investigated for corrosion protection of mild steel coupled with copper in 3.5% NaCl solution. EB/ER coating with 5-10 wt% EB had long-term corrosion resistance on both uncoupled steel and copper due to the passivation effect of EB on the metal surfaces. During the 150 immersion days, the impedance at 0.1 Hz for the coating increased in the first 1-40 days and subsequently remained constant above 10⁹ Ω cm², whereas that for pure ER coating fell below 10⁶ Ω cm² after only 30 or 40 days. Immersion tests on coated steel-copper galvanic couple showed that EB/ER coating offered 100 times more protection than ER coating against steel dissolution and coating delamination on copper, which was mainly attributed to the passive metal oxide films formed by EB blocking both the anodic and cathodic reactions. Salt spray tests showed that 100 μm EB/ER coating protected steel-copper couple for at least 2000 h.     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.     

Influence of natural inhibitor,pigment and extender on corrosion of polymer coated steel

Lupine (Lupinous albus L.) seeds extract was incorporated into a vinyl chloride–vinyl acetate copolymer based paint formulation to control steel corrosion in 0.5 M NaCl. Evaluation of this system included the use of electrochemical impedance spectroscopy (EIS) and a salt spray cabinet for accelerated aging tests. The EIS data demonstrated that highest protection was attained at a lupine threshold concentration of 0.025 g/L. Two white color pigments (ZnO and TiO₂) and three extenders (CaCO₃, mica and talc) were tested as paint additives. The accelerated aging tests showed that the coated steel panels containing TiO₂ had a high degree of blistering while those containing ZnO exhibited reasonable hiding power and better protection efficiency. Field tests indicated that the presence of TiO₂ enhanced the growth of fouling organisms over the coated steel surface.     

Synthesis and anticorrosion performance of poly(2,3-dimethylaniline)–TiO2 composite

Poly(2,3-dimethylaniline)–TiO₂ composite (PTC) was prepared by oxidative polymerization of 2,3-dimethylaniline in phosphoric acid medium with ammonium persulphate as oxidant. The composite was characterized by Fourier transformation infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). TiO₂ particles, rather being simply blended or mixed up, are encapsulated or entrapped into the polymer core, resulting in some significant improvement in its anticorrosion properties. Suitable coating with PTC was formed on steel using epoxy resin, and its corrosion resistance behavior was studied by open circuit potential (OCP) and electrochemical impendence spectroscopy (EIS) in 3.5% NaCl solution and also compared with that of PANI and poly(2,3-dimethylaniline) (P(2,3-DMA)). It has been found out that the coating containing PTC has got higher corrosion resistance than that of PANI and P(2,3-DMA).     

Impedance evaluation of permeability and corrosion of Al-2024 aluminum alloy coated with a chromate free primer

The corrosion of AA-2024 aluminum alloy protected with a chromate free primer is investigated after immersion in a 0.5 M NaCl aqueous solution. The water uptake by the coating increases continuously when the film, applied on an aluminum AA-2024 substrate, is placed in the 0.5 M NaCl solution. This increase is attributed to corrosion reactions taking place at the alloy/coating interface when water molecules reach the interface. The maximum water volume fraction absorbed by a similar coating applied on platinum substrate is 3.5 vol% and the permeability is 7.6 × 10⁻¹² m² s⁻¹. After 72 h immersion in the 0.5 M NaCl solution, the Nyquist representation of impedance data shows transmission line behavior that can be assigned to percolation pathway along the filler particles after water uptake. Charge transfer and diffusion of corrosion reactants and products occur, but no delamination was observed for immersion longer than 172 h. Furthermore, the coating resistance is still close to 10⁸ Ω cm⁻² after this immersion time. This accounts for the good protective performance of the coating.     

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.     

Performance of polyaniline pigmented vinyl acrylic coating on steel in aqueous solutions

Using electrochemical impedance spectroscopy method, the performance of vinyl acrylic coating containing polyaniline on steel in 0.1 N HCl, 3% NaCl and cement extract (pH 13.0) has been evaluated. The resistance of the paint coating in all the media has been found to decrease initially from 10⁸ to 10⁶ Ω cm². On subsequent exposure to the aqueous media, the resistance of the coating has been found to increase steadily. Further, the open circuit potential values have been found to shift in active direction initially and then move in noble direction with longer immersion period due to the passivating effect of polyaniline pigment.     

Studying the influence of nano-Al2O3 particles on the corrosion performance and hydrolytic degradation resistance of an epoxy/polyamide coating on AA-1050

The aim of this work was studying the effects of addition of Al₂O₃ nanoparticles on the anticorrosion performance of an epoxy/polyamide coating applied on the AA-1050 metal substrate. For this purpose, the epoxy nanocomposites were prepared using 1, 2.5 and 3.5 (w/w) pre-dispersed surface modified Al₂O₃ nanoparticles. Field-emission electron microscope (FE-SEM) and ultraviolet–visible (UV–Vis) techniques were utilized in order to evaluate the nanoparticles dispersion in the epoxy coating matrix. The anticorrosion performance of the nanocomposites was studied by electrochemical impedance spectroscopy (EIS) (in 3.5 wt% NaCl solution for 135 days immersion) and salt spray test for 1000 h. The coating resistance against hydrolytic degradation was also studied by optical microscope and Fourier-transform infrared spectroscopy (FTIR). Results obtained from FE-SEM micrographs and UV–visible spectra showed that the nanoparticles dispersed in the coating matrix uniformly with particle size less than 100 nm even at high loadings. Results revealed that nano-Al₂O₃ particles could significantly improve the corrosion resistance of the epoxy coating. Nanoparticles reduced water permeability of the coating and improved its resistance against hydrolytic degradation.     

Effects of powder size and metallic bonding layer on corrosion behaviour of plasma-sprayed Al2O3-13% TiO2 coated mild steel in fresh tropical seawater

This study focuses on the effects of powder size and Ni–Al bonding layer on the electrochemical behaviour of plasma-sprayed Al₂O₃-13% TiO₂ coating in fresh tropical seawater. The presence of the metallic bonding layer reduces the coating porosity and increases the surface roughness for both microparticle and nanoparticle coatings. The nanoparticle exhibits better corrosion rate of 1.9×10⁻⁶ mmpy compared to the microparticle coating, with a corrosion rate of 3.05×10⁻⁶ mmpy. However, the presence of the metallic bonding layer increases the corrosion rate for both micro and nanoparticle coatings. The corrosion mechanism for the coating with and without the metallic bonding layer is discussed in detail.     

Anticorrosive polyurethane paints with nano- and microsized phosphates

Two types of phosphate fillers (nanosized aluminum phosphate and microsized aluminum–zinc phosphate) were tested as anticorrosive fillers in 2 K solvent-borne polyurethane paints based on commercial acrylic resin with OH groups and an isophorone diisocyanate-type hardener. Three coating compositions containing commercial fillers (mica/quartz, TiO₂, wollastonite, talc) and also mentioned nanosized aluminum phosphate or microsized aluminum–zinc phosphate were prepared using a pearl-mill as well as a laboratory dissolver, applied onto a steel substrate and cured at room temperature for 14 days. An influence of the type and content of a phosphate filler on properties of polyurethane paints and coatings has been investigated. Incorporation of nanosized aluminum phosphate into coating compositions increases their viscosity while cured paints exhibit reduced adhesion to steel substrates. The results of corrosion tests in a salts spray chamber as well as immersion in an aqueous NaCl solution indicated that the paint system with 9.8 wt.% of applied nanofiller had similar protective properties to a polyurethane coat containing a higher dose (i.e. 15.6 wt.%) of commercial microsized aluminum–zinc phosphate.     

Highly protective performance of water-based epoxy coating loaded with self-doped nanopolyaniline synthesized under supercritical CO2 condition

In this study corrosion properties of water-based epoxy coating on carbon steel (CS) are improved by adding self-doped nano-polyaniline (SPAni) synthesized under supercritical carbon dioxide (ScCO₂) condition. The modified ScCO₂-synthesized SPAni using water-based polyamidoamine hardener results in formation of the water-based SPAni composite (Sc-WB). To obtain the water-based polyaniline epoxy coating (SP-WBE), the Sc-WB was mixed with epoxy resin in stoichiometric ratio. Applying SP-WBE on CS substrate resulted in high improvement in corrosion properties compared to the similar coating without SPAni. Formation of oxide layers and adhesion properties of SP-WBE at corrosive medium were evaluated using scanning electron microscope (SEM). The transmission electron microscope (TEM) was used to observe the distribution and particles size of nanopolyaniline in the final dried film. The anti-corrosion performance of water-based epoxy coating (blank sample) and SP-WBE coating on CS substrates were studied using salt spray standard test according to ASTM B-117, electrochemical impedance spectroscopy (EIS) and adhesion tests. EIS studies, after 1800 hrs of exposure to corrosive solutions, result in charge transfer resistance of 1.816E9 Ω and 8.64E7 Ω for SP-WBE and blank samples, respectively.     

咪唑啉季铵盐缓蚀剂改性蒙脱土/水性环氧纳米复合涂料

以油酸、二乙烯三胺和氯化苄为原料,合成了油酸基咪唑啉季铵盐缓蚀剂。通过FTIR、¹HNMR对其结构进行了表征,并离子交换至钠基蒙脱土(DK0)层间,制备了缓蚀剂改性蒙脱土(QACDK0)。通过XRD、TGA和UV-Vis对其结构、组成及层间缓蚀剂释放性能进行了表征。结果表明,咪唑啉季铵盐缓蚀剂约占QACDK0质量的38.96%,并将蒙脱土层间距由1.28 nm(DK0)扩大至3.98 nm(QACDK0)。利用DLS及Zeta电位对添加有QACDK0的水性环氧树脂进行了稳定性测试,其Zeta电位为–27.8 m V,具有较高的稳定性。电化学阻抗谱(EIS)测试表明,在腐蚀介质中浸泡30 d后,基于QACDK0制备的清漆漆膜仍具有2.29×10⁸?·cm²的高阻抗,表明涂层具有较好的耐腐蚀性。并且在耐中性盐雾测试中,QACDK0对应的防腐色漆耐盐雾时间最长,验证了该涂层具有良好的耐盐雾性能。     

Corrosion performance of waterborne epoxy coatings containing polyethylenimine treated mesoporous-TiO2 nanoparticles on mild steel

Waterborne epoxy coatings were modified by adding mesoporous-TiO₂ nanoparticles (meso-TiO₂). In order to achieve proper dispersion of meso-TiO₂ in the epoxy-based coating and make possible chemical interactions between meso-TiO₂ and polymeric coating, meso-TiO₂ was treated with polyethylenimine (PEI) of various molecular weights. Corrosion performance of mild steel coated specimens was investigated employing electrochemical impedance spectroscopy (EIS) and salt spray test. Coatings with meso-TiO₂/PEI (600 molecular weight) possessed the best corrosion performance among the coating specimens. The EIS results showed that the resistance value of coating with meso-TiO₂/PEI (600 molecular weight) was above 9.87 × 10⁷ Ω cm² which was higher than neat epoxy coating. Possible chemical interactions between polymeric matrix and treated nanoparticles caused high barrier properties and high degree of cross-linking.     

Study of the effect of mechanically treated CeO2 and SiO2 pigments on the corrosion protection of painted galvanized steel

The effectiveness of mechanically treated CeO₂ particles and SiO₂ particles as active fillers into an organic coating was investigated. For this purpose, different combinations of CeO₂ and SiO₂ particles were added to an epoxy-polyester polymeric matrix: mechanically treated CeO₂ particles, mechanically treated CeO₂/SiO₂ particles and mechanically treated SiO₂ powders (used for comparison). The particles were dispersed into the polymeric matrix and HDG steel panels were coated with the different paints. A strontium chromates containing paint was used as a reference to compare the performances of the other samples. The salt spray results proved the good performance of coatings containing combinations of ceria and silica especially where these had been mechanically treated in a co-milling operation. The paint containing only the mechanically treated SiO₂ particles showed a fairly good resistance in the salt spray chamber considering the scratched samples. The EIS measurements evidenced the good corrosion protection properties of the paints containing the different combinations of mechanically treated CeO₂ and SiO₂ particles. After about 1000 h of immersion in 0.1 M NaCl solution, the samples containing the mix of mechanically treated CeO₂/SiO₂ particles showed impedance values which were comparable with the chromate control sample. The cathodic polarization tests evidenced the low extent of detachment of the coating containing the mix of mechanically treated CeO₂/SiO₂ particles. The electrochemical characterization and neutral salt spray test results proved the effectiveness of the mechanical treated cerium (IV) oxides treated together with SiO₂ as active pigments to improve the corrosion protection of the substrate. The reasons for the synergistic effect of the milled (together or separately) SiO₂ and CeO₂ particles was not clear at all, but a few hypothesis were discussed.     

Local electrochemical impedance measurements on inclusion-containing stainless steels using microcapillary-based techniques

MnS inclusions are good precursor sites for pitting corrosion of stainless steel. The objective of this paper was to quantify the passive properties of resulfurized stainless steel after immersion in chloride media. This was done by combining microcapillary techniques with electrochemical impedance spectroscopy and numerical analysis (specific equivalent circuit). It was shown that sulfur species produced in the electrolyte during the dissolution of inclusions react with the native passive film to CrS and FeSO₄. Local electrochemical impedance spectroscopy measurements provided data describing the behaviour of the affected matrix at the microscale. For example, the value of the charge transfer and migration of point defects resistance decreases from 51,700 Ω cm², in sites free of any metallurgical heterogeneity down to 12,200 Ω cm², in sites containing a high density of inclusions. It was also shown that the integrity of the microcapillary can be altered by the presence of high quantity of sulfur in the electrolyte. Local impedance data allowed the detection of such problems.     

Characterization and anticorrosive properties of poly(2,3‐dimethylaniline)/TiO2 composite synthesized by emulsion polymerization

Poly(2,3‐dimethylaniline)/TiO₂ composite (PTC) was prepared by emulsion polymerization using dodecyl benzene sulfonic acid as emulsifier and dopant. The structure of PTC was characterized by Fourier transformation infrared spectroscopy, wide‐angle X‐ray diffraction, and field emission scanning electron microscopy. Effect of TiO₂ content on the PTC properties was studied by tafel polarization curves, electrochemical impedance spectroscopy, polymerization yield, and cyclic voltammetry measurements. The results showed that the anticorrosion property and electrochemical activity of PTC reached a maximum level when the content of TiO₂ was 15%. Epoxy coatings containing poly(2,3‐dimethylaniline) (P(2,3‐DMA)) and PTC, respectively, were painted on steel and accelerated electrochemical corrosion tests were performed to evaluate the anticorrosion property of the coatings in 3.5% NaCl solution. The results showed that the PTC coating had higher corrosion resistance than that of P(2,3‐DMA). POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Corrosion protection of steel by sulfo-doped polyaniline-pigmented coating

This work presents the corrosion protection behaviour of mild steel in neutral saline conditions (salt spray/immersion) by using coatings based on chlorinated rubber and benzene-sulfonate (BS) or lignosulfonate (LS)-doped polyaniline (PANI). Standardized accelerated (salt spray) and immersion tests were performed to assess the protective performance of the coatings. Analysis and interpretation of the experimental data (i.e., EIS, potentiodynamic data and visual observations) showed that both PANI-BS and PANI-LS inhibit corrosion of painted steel exposed to a 3.5% NaCl solution. Among the tested concentrations (0.5, 1.5 and 3 wt.%), the greatest inhibition was observed at low concentration of PANI-BS (0.5%). Samples with higher PANI-BS loadings (1.5 and 3%) appear severely corroded after 560 h of salt spray exposure, which was related to the release of corrosive benzene sulfonic acid. On the contrary, the coatings with lignosulfonate doped PANI performed well both in the salt spray and immersion tests, especially at the highest PANI concentrations (1.5 or 3%). With regard to the healing properties, PANI-LS with the lowest conductivity (1 S cm⁻¹) performed the best.     

Facile synthesis of mesoporous Ag-loaded TiO2 thin film and its photocatalytic properties

Ag nanoparticles highly dispersed into TiO₂ thin films are synthesized via a remarkably simple one-pot route in the presence of a P123 triblock copolymer as template directing and reducing agents, where the reduction of Ag⁺ to Ag⁰ by in situ heat-induced reduction through the oxidation of template at 400 °C and the controlled polymerization of TiO₂ take place simultaneously. The obtained mesoporous Ag/TiO₂ films deposited on soda-lime glass were optically transparent and crack-free. SEM and Kr adsorption clearly prove that Ag/TiO₂ films at different Ag contents are mesoporous with large surface area and regularly ordered mesopores and the thickness of the obtained films is ∼280 ± 20 nm. The pristine TiO₂ film exhibits a specific surface area of 63 cm²/cm² and specific pore volume of 0.013 mm³/cm² that it is decreased to 42 cm²/cm² and 0.010 mm³/cm² respectively as a result of Ag-loaded mesoporous TiO₂. The newly prepared photocatalysts Ag/TiO₂ films were evaluated for their photocatalytic degradation of 2-chlorophenol as a model reaction. It was found that the meso-ordered Ag/TiO₂ films are more photoactive 8 times than nonporous commercial photocatalysts Pilkington Glass Activ™. The recycling tests indicated that Ag/TiO₂ films was quite stable during that liquid-solid heterogeneous photocatalysis since no significant decrease in activity was observed even after being used repetitively for 10 times, showing a good potential in practical application. In general, the cubic mesoporous Ag/TiO₂ nanocomposites are stable and can be recycled without loss of their photochemical activity.     

Advanced anticorrosive coatings prepared from electroactive polyimide-TiO2 hybrid nanocomposite materials

In this study, we present the first preparation and corrosion protection studies of a series of electroactive polyimide-TiO₂ (EPTs) hybrid nanocomposite materials containing conjugated segments of electroactive amino-capped aniline trimer (ATs) and TiO₂ nanoparticles of ∼10 nm in diameter. Redox behavior of as-prepared EPTs hybrid materials was identified by electrochemical cyclic voltammetry (CV) studies. Higher concentration of TiO₂ component in as-prepare corresponding EPTs was found to reveal better corrosion protection effect on cold-rolled steel (CRS) electrode based on sequential electrochemical corrosion measurements in 5 wt.% NaCl electrolyte. Enhancement of corrosion protection of EPTs coatings on CRS electrode could be interpreted by following three possible reasons: (1) Electroactive polyimide (EPI) could act as a physical barrier coating. (2) The redox catalytic capabilities of ATs units existed in EPTs may induce the formation of passive metal oxide layers on CRS electrode. (3) The well-dispersed TiO₂ nanoparticles in EPTs matrix could act as effective hinder to enhance the oxygen barrier property of EPTs.