Electrochemical impedance spectroscopy investigation of the corrosion at metallic substrates covered by organic coatings

The corrosion protection characteristics of an epoxy-polyamide coating were investigated by electrochemical impedance spectroscopy in immersion tests performed in a 3.0% NaCl solution. Carbon steel and galvanized steel substrates were employed. A porous film was produced on the metallic substrates, which allows for electrochemically reactive areas to be developed inside the pores. An effective corrosion-resistant system was produced in the case of the galvanized steel substrates, due to the precipitation of zinc-containing corrosion products that contribute to the sealing of the coating. Conversely, no effective protection was found for carbon steel specimens, since in this case the local accumulation of the corrosion products causes swelling of the coating.     

Corrosion protection of galvanized steel by polyimide coatings: EIS and SEM investigations

Coatings of two types of polyimides (PI), as poly(4,4′-oxydiphtalic anhydride-co-2,5-bis(4,4′-methylenedianiline)-1,4-benzoquinone) (AQ) and poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PM), were synthesized on galvanized steel panels and studied and compared in terms of chemical structure, microstructure and corrosion performance in 0.5 M NaCl solution. Infra-red spectroscopy, scanning electron microscopy and in situ electrochemical impedance spectroscopy were employed in the investigations. The results showed that, although both studied PI coatings provided the galvanized steel substrate with corrosion protection during the test period, there were evident differences in electrochemical behaviour of the coatings, which could be primarily explained by the different nanostructures. FE-SEM examinations revealed AQ PI coating to be heterogeneous and discontinuous but PM PI coating homogeneous and continuous in nanostructure. Electrochemical behaviour of AQ PI coated galvanized steel obeyed that of a defect-containing coating and indicated gradual decrease in protectivity. In contrast, PM PI coating behaved like a defect-free coating and it provided the galvanized steel substrate with effective corrosion protection all through the 960 h test. The explanations for these observations and the mechanisms of coating damage are discussed in this paper.     

Electrochemical and morphological properties of zirconium conversion coating in the presence of nickel ions on galvanized steel

A hexafluorozirconic acid-based conversion coating was applied on a galvanized steel substrate and the influence of nickel ion from nickel sulfate solution (in zirconium solution and in a separate solution) on the corrosion resistance behavior and morphology of zirconium conversion coating was investigated. Electrochemical impedance spectroscopy and DC polarization were conducted in 3.5 wt% NaCl solution in order to optimize practical conditions of zirconium conversion coating and NiSO₄ solution on the galvanized steel substrate. Field emission scanning electron microscopy and X-ray photoelectron spectroscopy were employed to study the morphology and composition of the coated surfaces. Results revealed that the conversion coating obtained from solution containing zirconium and nickel ions (Zr + Ni) did not improve corrosion resistance and uniformity of the coating in comparison with Zr conversion coating in optimized condition. However, a positive effect was obtained from samples coated with separate solutions of zirconium and nickel (Zr–Ni). Improved corrosion resistance and morphology of Zr-based conversion coating were observed in Ni²⁺ concentration, pH, and immersion time of 10 g/L, 6 and 300 s, respectively. Morphology and surface composition analysis proved that two separate layers of conversion coating containing zirconium, zinc, and nickel oxide/hydroxide compounds were formed in the case samples that were treated by separate solutions. This led to better uniformity and higher thickness of the coating. Finally, adhesion strength of epoxy organic coating on galvanized steel with and without conversion coating was investigated by pull-off measurement. Zr–Ni conversion coating in optimum conditions had a positive effect on adhesion of organic coating in comparison with blank sample and samples pretreated with Zr and Zr + Ni conversion coatings through increased surface roughness and physical interlocking.     

Resistance of metallic substrates protected by an organic coating containing glass flakes

The resistance against corrosion of an epoxy-polyamine-based coating immersed in a 3 wt.% sodium chloride solution was investigated by electrochemical impedance spectroscopy (EIS). The organic coating contained glass flakes as pigment in order to enhance its barrier characteristics. The data show that this coating is more strongly adhered and exhibits higher protection characteristics when applied onto carbon steel substrates than on galvanized steel. Though the capacitance of the coating (C_C) does not show any appreciable variation with immersion time, the resistance (R_PO) of the film is observed to increase with time upon immersion. The analysis of the data sustains that the organic film behaves as a porous, non-barrier coating. Two time constants are observed even at earlier exposures, and the improved corrosion resistance developed after the coating system was exposed to the test electrolyte is considered to originate from the precipitation of corrosion products within the pores in the film.     

Effects of coating thickness and surface treatment on the corrosion protection of diglycidyl ether bisphenol-A based epoxy coated carbon steel

The corrosion resistance of carbon steel specimens was compared, using different surface treatment methods such as blasting and zinc phosphate treatment on carbon steel followed by application of different coating thickness. Specimen surface morphology was observed by SEM. The corrosion performance of epoxy coated carbon steel was examined by electrochemical impedance spectroscopy (EIS), along with immersion test in 0.5N-NaCl solution and NORSOK M 501 cyclic test, respectively. EIS results showed that higher thickness of epoxy coating and zinc phosphate treatment on carbon steel showed better corrosion protection than rest of the specimens. Specimens with no treatment and blasting treatment followed by epoxy coating, showed poor corrosion protection. Results of NORSOK M 501 cyclic test showed similar trend as those of EIS results however degradation of specimens was more severe than those from immersion test.     

Corrosion inhibition of aluminum by organic coatings formulated with calcium exchange silica pigment

One of the first commercial ion-exchange anticorrosive pigments to be developed was Shieldex^® (Si/Ca). Its proposed corrosion protection mechanism, based on the retention of aggressive cations and the subsequent release of calcium cations, has created certain controversy. A number of studies have focused on the anticorrosive behavior of this pigment on carbon steel and galvanized steel to replace chromates (Cr⁶⁺) as inhibitor pigment, but none has considered its performance on aluminum or aluminum alloys. In this research, alkyd coatings have been formulated with Si/Ca pigment at different concentrations and applied on aluminum 1050 (Al 99.5%) specimens. These specimens have then been subjected to accelerated tests (condensing humidity, salt spray, and Kesternich) and natural weathering in atmospheres of different aggressivity. Corrosion performance has been also evaluated in the laboratory by electrochemical impedance spectroscopy. The study has also considered an organic coating with zinc chromate anticorrosive pigment for comparative purposes. The results obtained with organic coatings formulated with Si/Ca pigments confirm that they provide corrosion protection of the underlying aluminum substrate, even improving the behavior of the reference zinc chromate in some environmental conditions.     

Effect on temporary protection and adhesion promoter of silane nanofilms applied on electro-galvanized steel

In this paper, the effectiveness of γ-mercaptopropyltrimethoxysilane (MTMO) films as temporary corrosion protection and adhesion promoter on electro-galvanized steel was studied. The films were synthesized from hydrolyzed MTMO with ethanol or methanol, applied by immersion on electro-galvanized steel and cured under different conditions. The porosity of the coating was evaluated by cyclic voltammetry, the corrosion behavior by polarization curves and the protection degree by exposure in the humidity and prohesion chambers. The films were characterized by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). From the obtained experimental results, it was concluded that this protection is markedly affected by the coating curing conditions and the alcohol used in the hydrolysis. MTMO is a good temporary protector against electro-galvanized steel corrosion in high humidity environment but it is less effective in environments containing aggressive ions such as Cl⁻ and SO₄⁻².In a second stage, pretreated samples were coated with an alkyd anticorrosive paint and exposed to the salt spray chamber. Dry adhesion tests as well as SEM and EDS studies were also done in order to know the nature of the disbonding fails (adhesion or cohesion).     

Laboratory evaluation of corrosion resistance at metallic substrates by an organic coating: delamination effects

The corrosion behaviour of an epoxy-polyamide primer applied on galvanized steel specimens during immersion in 3% NaCl aqueous solution was examined by electrochemical impedance spectroscopy (EIS). The investigation of both intact and defective coatings allowed for the comparison of their electrochemical behaviours in order to assess the anticorrosive characteristics of the system. The impedance response of the intact coating was found to correspond to a porous film presenting localised electrochemically active areas, in which the precipitation of zinc-containing corrosion products contributes to the sealing of the coating. Conversely, scribed defects cannot be spontaneously sealed and no effective protection of the metal can be achieved.     

Anticorrosion epoxy coating enriched with hybrid nanozinc dust and halloysite nanotubes

In this study, the performance of an epoxy coating with hybrid nanozinc dust and halloysite nanotube (HNT) fillers on the corrosion protection of a carbon steel substrate was investigated. The epoxy resin was mixed with a constant amount of nanozinc dust (1%) and different contents of HNTs (0, 0.5, 1, and 1.5%) with a high speed mixer. Fourier transform infrared spectroscopy and thermogravimetric analysis were used to analyze the interactions between the components in the coating material and the thermal stability of the epoxy coating, respectively. Open‐circuit potential, salt spray testing, and microscopy were also used to assess the corrosion resistance of the carbon steel substrate coated with these coating materials. The incorporation of nanozinc in the epoxy coating enhanced the corrosion protection of the carbon steel substrate compared with the pure coating. Furthermore, HNTs further enhanced the corrosion protection. The best protection was achieved when 1% nanozinc and 1% HNT were used. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 955‐960, 2013     

Corrosion protection properties of silane pre-treated powder coated galvanized steel

Silane based products are becoming an interesting material for pre-treatment deposition, because, for the environmental compatibility, they can be used as substitutes of traditional pre-treatments like chromates. Silanes have been studied as new pre-treatments before organic coating deposition for many different metals, including aluminium, copper and zinc.In this work, some results concerning the properties of water-based silane pre-treatments on galvanized steel will be presented.Galvanized sheets obtained by continuous hot dip process were considered. A silane based bath containing a mixture of three different silanes were used for the pre-treatment deposition (Glycidoxypropiltrimethoxysilane, Tetraethoxysilane and Methyltriethoxysilane).The obtained pre-treatments were characterized by SEM observations, FT-IR and ToF-Sims analysis. The corrosion protection properties of the pre-treated galvanized samples were studied using industrial accelerated tests (like salt spray exposure) and electrochemical measurements (polarization curves and electrochemical impedance spectroscopy (EIS) measurements), as a function of the different curing conditions. The pre-treated galvanized sheets were further coated with an epoxy-polyester powder coating, in order to verify the adhesion promotion properties and the corrosion protection performances of the complete protective system.The coated samples were characterized by EIS measurements with artificial defect in order to study the interfacial stability (adhesion) in wet conditions and monitor the coating delamination.The electrochemical data were compared with adhesion measurements obtained by cathodic delamination tests. The electrochemical tests showed that the silane layer acts not only as a coupling agent between the inorganic substrate and the organic coating, but it also ensures a good barrier effect against water and oxygen.     

Compatibility between cataphoretic electro-coating and silane surface layer for the corrosion protection of galvanized steel

The compatibility between a cataphoretic electro-coating and a silane layer applied on galvanized steel was evaluated by performing electrochemical impedance measurements on coated and uncoated samples. During electro-deposition, the water electrolysis induces hydrogen production. This process can induce degradation or destruction of the silane layer. This process was simulated by reproducing the application conditions of electro-coating in an aqueous solution of same pH (6) and conductivity (1600 μS) than the electro-coating bath, but without any pigments and binder. A current of 2 mA/cm² was applied between the sample and the counter-electrode during 10 and 20 s. These conditions are representative of the mean real application conditions just before the coating formation. The loss of the barrier effect offered by the silane layer was evaluated by EIS before and after simulation. This simulation shows whether it is possible to conveniently design the properties of the silane layer to maintain its protection and adhesion promotion properties after polarization. The barrier properties and the water uptake of the electro-coated samples were evaluated by EIS as a function of immersion time in a sodium chloride solution (0.1 M). The coated silane pre-treated samples show a good behaviour compared to the samples coated without pre-treatment. By properly managing the deposition conditions of sol–gel films it is possible to obtain cataphoretic coating with improved corrosion resistance. Silane sol–gel films of different thicknesses and curing temperature were produced. It was demonstrated that a 120 nm thick silane sol gel film cured at 180 °C ensures a very good compatibility with the electro-coat. In fact, this system shows a very high corrosion resistance even after 50 days of immersion in a sodium chloride solution. Also the resistance in the salt spray chamber of the electro-coated thin silane layer cured at 180 °C is remarkable. The results confirm that, if conveniently designed, silane sol–gel film properties, the silane layer is a good adhesion promoter of the cataphoretic coating on galvanized steel and this property is maintained for long exposure times.     

Resistance to corrosion of galvanized steel covered with an epoxy-polyamide primer coating

The resistance to corrosion provided by an epoxy-polyamide primer attached to a galvanized steel panel was assessed by electrochemical impedance spectroscopy. Three different coating thicknesses were tested in this work, namely 100, 200 and 500 μm, which were applied on panel sections cut-off from overhead electrical transmission-line towers. Corrosion tests were performed by exposing the painted coupons to a 3.0% NaCl aqueous solution in a horizontal flat-cell. Changes in the impedance characteristics of the systems were found to occur as a function of the exposure time in all the three cases, though their evolution with time showed marked differences which derived directly from the different thicknesses of the coatings. With the thinnest coating considered, the primer film could not provide an effective protection for the metal that underwent corrosion as a result of the delamination process. On the contrary, when the coating film was sufficiently thick, effective protection of the metallic substrate was provided by the epoxy-polyamide film.     

A new smart coating of polyaniline–SiO2 composite for protection of mild steel against corrosion in strong acidic medium

Organic coating approaches for corrosion protection with inherently conducting polymers have become important because of restriction on the use of heavy metals and chromates in coatings due to their environmental problems. The present work is directed towards the synthesis of polyaniline (PANI) and polyaniline–SiO₂ composites (PSCs) by chemical oxidation polymerization in the presence of phosphoric acid and evaluation of synthesized PANI and PSCs for protection of mild steel from corrosion in a strong aggressive medium (i.e. 1.0 mol L^–1 HCl). A suitable coating with PSC was formed on mild steel using epoxy resin by the powder coating technique. A comparative study of the corrosion protection efficiency of mild steel coated with PANI and PSC in 1.0 mol L^–1 HCl solution was evaluated using the Tafel extrapolation, chrono‐amperometry and weight loss methods. The PSC coating showed that a significant reduction in the corrosion current density reflects the better protection of mild steel in an acidic environment. Higher protection efficiency up to 99% was achieved by using PSC‐coated mild steel at 6.0 wt% loading of PSC in epoxy resin. The coating performance and corrosion rate of mild steel were investigated by using immersion of polymer‐coated mild steel in 1.0 mol L^–1 HCl for 60 days and indicated that PSC‐coated mild steel showed better performance from corrosion than PANI in an acidic medium.© 2012 Society of Chemical Industry     

Reduction of cathodic delamination rates of anticorrosive coatings using free radical scavengers

Cathodic delamination is one of the major modes of failure for anticorrosive coatings subjected to a physical damage and immersed in seawater. The cause of cathodic delamination has been reported to be the result of a chemical attack at the coating–steel interface by free radicals and peroxides formed as intermediates in the cathodic reaction during the corrosion process. In this study, antioxidants (i.e., free radical scavengers and peroxide decomposers) have been incorporated into various generic types of coatings to investigate the effect of antioxidants on the rate of cathodic delamination of epoxy coatings on cold rolled steel. The addition of <5 wt% free radical scavengers to epoxy coatings improved the resistance toward cathodic delamination by up to 50% during seawater immersion, while peroxide decomposers had a limited effect. Testing using substrates prepared from stainless steel, copper, aluminum, galvanized steel, and brass also showed a reduction in the rate of cathodic delamination when the coating was modified with a free radical scavenger. The protective mechanism of free radical scavengers investigated for the primers are similar to that of antioxidants used for protection against photochemical degradation by UV-radiation of top coatings. Both substrate corrosion and degradation of a coating exposed to UV-radiation lead to the formation of free radicals as reactive intermediates.     

Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90–100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

Durability of Adhesive Bonds to Zinc-Coated Steels: Effects of Corrosive Environments on Lap Shear Strength

The effects of corrosive environments on adhesive bonds to electro-galvanized, zinc/aluminum alloy coated, coated electro-galvanized, and cold-rolled steels have been investigated. Bonds prepared using a rubber-modified dicyandiamide-cured epoxy adhesive, an epoxy-modified poly(vinyl chloride)-based adhesive, an acrylic-modified poly(vinyl chloride)-based adhesive a one-part urethane adhesive, and a two-component epoxy-modified acrylic adhesive were exposed under no-load conditions to constant high humidity or cyclic corrosion exposure for 50 days or 50 cycles (10 weeks) respectively.

Over the course of this study, exposure to constant high humidity had little effect on lap shear strength for any of the systems studied. Bond failures were initially cohesive, and with few exceptions remained so.

Bond strength retention under the cyclic corrosion exposure conditions employed was strongly dependent on adhesive composition and on substrate type. On galvanized substrates, lap shear strengths for the poly(vinyl chloride)-based adhesives were reduced by 90-100% during the course of the corrosion exposure, and a change in the mode of bond failure (from cohesive to interfacial) was observed. On the coated electro-galvanized steel substrate, the poly(vinyl chloride)-based adhesives showed about 50% retention in lap shear strength and a cohesive failure throughout most of the corrosion test. The dicyandiamide-cured epoxy adhesive used in this study generally showed the best lap shear strength retention to zinc-coated substrates; bonds to cold-rolled steel were severely degraded by corrosion exposure. The performance of the acrylic and urethane adhesives were intermediate to the dicyandiamide-cured epoxy and poly(vinyl chloride)-based adhesives in strength retention.     

Failure mechanism of thin Al2O3 coatings grown by atomic layer deposition for corrosion protection of carbon steel

Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50 nm) Al₂O₃ coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7 nm h⁻¹ in neutral 0.2 M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix.     

The effect of chromated and organic layers on corrosion resistance of galvanized steel sheets

Chromated zinc steel sheets have been used widely for corrosion resistance performance in various waters. The coating system includes a chromated layer and both a primer and topcoat, a commonly applied system for better corrosion performance. Electrochemical impedance spectroscopy results show that the corrosion resistance of chromated zinc is due to its passivity after water uptake during the exposure. In galvanized steel sheets with a primer, the electrolyte solution can only reach the metallic substrate through the coating pores; thus, a double layer could build up locally at the bottom of the pores, resulting in a good corrosion resistance for the sheet. On the other hand, the high-pore-resistance system of primer and topcoat provides no evidence of corrosion even after 8 weeks’ exposure.     

The effect of zirconia ions on corrosion performance of sol–gel coated galvanized steel

Currently, galvanized steel is treated with hexavalent chrome passivation. Sol–gel coating has been found to be a potential replacement for the hazardous hexavalent chrome passivation treatment. The aim of this work is to study the effect of zirconyl nitrate on corrosion behavior of sol–gel coating. Aminopropyl-trimethoxysilane and 3-glycidoxypropyltrimethoxysilane were employed as precursors to prepare the sol–gel-based silane coating. The sol–gel film was deposited on galvanized steel sheet by dip coating method. The chemical properties of sol–gel solution and coated films were analyzed by infrared spectroscopy. Morphology of the film was characterized by scanning electron microscope. The corrosion resistance of the coated samples was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization curve, and salt spray test. The results indicated that zirconia-doped coatings have better corrosion resistance in comparison with their undoped counterparts. The coating doped with 0.5% zirconyl nitrate provides better corrosion protection due to the inhibitive action of zirconia ion.     

The mode of action of chromate inhibitor in epoxy primer on galvanized steel

Investigations of the mechanism of the protective action of strontium chromate pigment in an epoxy primer were carried out with electrochemical impedance spectroscopy (EIS), atomic absorption spectroscopy (AAS), scanning reference electrode techniques (SRET) and water uptake measurements. Epoxy primers applied to galvanized steel were studied in a corrosion environment which models the atmospheric precipitation of European countries. Corrosion and electrochemical properties of samples of bare galvanized steel and coated galvanized steel were investigated. It was established that the protective function of the chromate in the primer is primarily due to a cathodic/mixed inhibition of the surface of galvanized steel in defect areas of the polymer coating. It is suggested that the process of leaching of chromate ions from epoxy primer into the environment takes place because the decrease in pH at anodic defect sites causes the destruction of the primer film and accelerates the dissolution of the chromate pigment.