Influence of Si nanoparticles on the electrochemical behavior of organic coatings on carbon steel in chloride environment

Scanning electrochemical microscopy (SECM) is an excellent technique to detect electrochemical processes with high spatial resolution. In this work, the effect of silicon (Si) nanoparticles on the corrosion protection performance of epoxy-coated steel was examined by electrochemical impedance spectroscopy (EIS) and SECM analysis. The EIS was performed in continuous immersion in 0.1?M NaCl_(aq) solution. The addition of Si nanoparticles increased the coating film resistance (R _f) and the charge transfer resistance (R _ct) of coated steel. SECM mapping and line scan analysis was performed in order to estimate the coating performance with Si nanoparticles in 0.1?M NaCl_(aq) solution. SECM results indicated that the tip current at ?0.70?V was decreased by the addition of Si nanoparticles in epoxy film. These results suggested that the dissolved oxygen (DO) was consumed by anodic dissolution of Si nanoparticles. Surface analysis showed that the Si was enriched at the scratched region of the coated steel after a corrosion test. From these results, Si was dissolved as Si ⁿ⁺ and transferred to the scratched area, and then consumed the DO in the solution. Thus, the anodic dissolution of Fe at the scratched area was suppressed by the Si nanoparticles, which implies the sacrificial effect of Si from the coating against the steel corrosion. Hence, it was concluded that the Si nanoparticles had a beneficial effect on enhancing the corrosion resistance of the coated steel.     

Performance of zinc phosphate coatings obtained by cathodic electrochemical treatment in accelerated corrosion tests

The formation of zinc phosphate coating by cathodic electrochemical treatment and evaluation of its corrosion resistance is addressed. The corrosion behaviour of cathodically phosphated mild steel substrate in 3.5% sodium chloride solution exhibits the stability of these coatings, which lasts for a week's time with no red rust formation. Salt spray test convincingly proves the white rust formation in the scribed region on the painted substrates and in most part of the surface on unpainted surface. The protective ability of the zinc corrosion product formed on the surface of the coated steel is evidenced by the decrease in the loss in weight due to corrosion of the uncoated mild steel, when it is galvanically coupled with cathodically phosphated mild steel. Potentiodynamic polarization curves reveal that E_corr shifts towards higher cathodic values (in the range of −1000 to −1100 mV versus SCE) compared to that of uncoated mild steel and conventionally phosphated mild steel substrates. The i_corr value is also very high for these coatings. EIS studies reveal that zinc dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the non-metallic nature of the coating is progressively increased due to the formation of zinc corrosion products, which in turn enables an increase in corrosion resistance with increase in immersion time. The zinc corrosion products formed may consist of zinc oxide and zinc hydroxychloride.     

Comparison of corrosion protection between double strands of polyaniline and poly-o-anisidine with poly(acrylic acid-co-acryl amide) on steel

Double strands of polyaniline (PAn) and poly(o-anisidine) (POAn) with poly(acrylic acid-co-acryl amide) (PAA-co-AA) were successfully prepared on steel as undercoating, by immersion of the pretreated surfaces into a PAn: (PAA-co-AA) and POAn: (PAA-co-AA) saturated DMF solution separately. The undercoatings formed on the steel were characterized by Fourier transform infrared spectroscopy (FTIR) techniques. A commercial paint (Nippon Paint, nonadded Chrome) was used as topcoating. Electrode/electroactive polymer/paint/electrolyte system was studied by electrochemical impedance spectroscopy (EIS). The EIS studies show that during the first 18 days immersion time in 3.5% solution of NaCl, paint/PAn coating has better corrosion resistance than paint/POAn coating while in the final week of immersion time, the pore resistance (R _po) and coating capacitance (C _c) of paint/POAn are higher and lower than the paint/PAn, respectively.     

Study on the corrosion behavior of reinforcing steel in cement mortar by electrochemical noise measurements

The corrosion behavior of reinforcing steel in cement mortar has been studied by electrochemical noise (EN) compared with the electrochemical impedance spectroscopy (EIS). The wavelet transform, as well as the statistical methods including the standard deviation of current noise (σ_I) and noise resistance (R_n), has been employed to analyze the EN data of reinforcing steel in mortar. It is revealed that there exist three different corrosion stages of reinforcing steel in cement mortar, including a competition process between breakdown and repassivation of passive film, a pitting development and an active corrosion during the 20 cyclic immersion and drying tests. The energy distribution plot (EDP) is able to provide useful information about the dominant process for the different corrosion stages.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Monitoring the degradation of a high solids epoxy coating by means of EIS and EN

This paper reports a study of the degradation processes suffered by steel samples painted with a high solid content epoxy coating. Because this coating shows a high resistance when exposed to NaCl solutions, HCl solutions were employed to accelerate the corrosion processes. Macroscopic images were used to observe the coating degradation. Then electrochemical techniques, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were employed to monitor the corrosion behaviour of the system studied. A close correlation was found between EIS and EN data. Several parameters were estimated using these techniques: R_po, R_ct, C_c, C_dl and Z_0.1 Hz using EIS, and R_n using EN. In addition, a new parameter estimated by means of EN was employed, Z_0.1 Hz(EN). The evolution of all these parameters with time enabled the effective monitoring of the degradation stage of the coating.     

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.     

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.     

AC impedance spectroscopy study of the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution

The corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution at the corrosion potential (E_corr) was investigated using electrochemical impedance spectroscopy (EIS), environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The results showed that when the immersion time was less than 18th, general corrosion occurred on the surface and the main corrosion products were hydroxides and sulfates. The film coverage effect was the main mechanism for the corrosion process of AZ91 alloy. At this stage, the matrix had a better corrosion resistance. With the increasing immersion time, pitting occurred on the surface. At this stage, the corrosion process was controlled by three surface state variables: the area fraction θ₁ of the region controlled by the formation of Mg(OH)₂, the area fraction θ₂ of the region controlled by the precipitation of MgAl₂(SO₄)₄·2H₂O, and the metastable Mg⁺ concentration C_m.     

Corrosion Protection of Stainless Steel by Poly(Carbazole-co-pyrrole) Films Deposited on TiO2 Sol–Gel Film

The poly(carbazole-co-pyrrole) copolymer was synthesized on TiO₂ sol–gel precoated 304 stainless steel (TiO₂) by cyclic voltammetry in tetrabutylammonium perchlorate containing acetonitrile solution. The synthesized coating was characterized by attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy, and solid-state conductivity measurements. Corrosion protection behavior of the TiO₂/poly(carbazole-co-pyrrole)-coated steel was evaluated by open circuit potential–time curves, potentiodynamic polarization, and electrochemical impedance spectroscopy methods. Corrosion test results showed that TiO₂/poly(carbazole-co-pyrrole) composite film enhanced corrosion resistance of stainless steel up to 50 days of immersion in 0.1M HCl corrosive medium.     

Effects of nanocrystallization on the corrosion behavior of 309 stainless steel

Nanocrystallized (NC) 309 stainless steel (309SS) coating has been fabricated on glass substrate by DC magnetron sputtering. The coating, with an average grain size less than 50 nm, had ferritic (bcc) structure rather than the austenitic (fcc) structure of the bulk steel. The electrochemical corrosion behavior of the NC coating and the bulk steel in solutions of 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ was investigated by using potentiodynamic polarization, potentiostatic polarization and AC impedance techniques. The results showed that the corrosion behavior of the NC 309SS coating and 309SS bulk steel depended on the composition of the solutions. In the Na₂SO₄ solution there was only a little difference between the corrosion resistance of the passive films on the NC coating and the bulk steel. However, in the solution with chloride ions, the localized corrosion resistance of 309SS was greatly enhanced by nanocrystallization due to the formation of a compact and stable passive film on the NC coating. The electronic structure of the passive film formed on the NC coating and on the bulk steel was analyzed by means of capacitance measurements, and a corrosion mechanism is proposed.     

In-situ generation and application of nanocomposites on steel surface for anti-corrosion coating

Thin organic coatings directly on steel sheets provide excellent barrier protection in saline environment and meet deformability demands, but fail in providing active corrosion protection. We have put an effort to solve this problem by formulating composite coatings using in-situ generation of metal oxide nanoparticles (NPs) in the polymer matrix. Here we present a new synthesis method of high performance polyetherimide composite with TiO₂, MgO, and Al₂O₃ nanoparticles and their application for anti-corrosion coatings in saline environment. We observed that in-situ synthesis of these metal oxide NPs in the polymer curing process leads to evenly distribution and uniform size of nanoparticles. Thermo-mechanical property was analyzed for these three kinds of free-standing composite film to assess elasto-plastic behaviour and compared to mother polymer film. Results indicated that thermal stability and elastic behaviour of composites film are not affected to the great extent by the presence of NPs. The potentiodynamic and the electrochemical impedance studies on these composite coated steel panels were carried out to identify active–passive behaviour. Results showed active corrosion protection from nanocomposite coating based on TiO₂ and barrier protection was noticed from nanocomposite coating based on MgO and Al₂O₃.     

A novel non-skid composite coating with higher corrosion resistance

In this work, low-pressure cold-sprayed Ni-Zn-Al₂O₃ intermediate layers were deposited between supersonic–plasma-sprayed NiCr-Cr₃C₂ surface layers and underlying low-carbon steel layers to form a sandwich structure that enhances the corrosion resistance of non-skid NiCr-Cr₃C₂ coatings. The corrosion performance of these bi-layer non-skid coatings and that of a single-layer coating were investigated through electrochemical measurements and observations of their corrosion morphologies. The novel non-skid coating with a top layer possessing a fine powder grain size exhibited the best corrosion resistance because of the pseudopassivation of the interlayer and physical barriers created by the corrosion process. The intermediate layer substantially improved the corrosion resistance of the non-skid coatings.     

Excellent corrosion protection performance of epoxy composite coatings filled with silane functionalized silicon nitride

Silicon nitride was firstly used as anticorrosive pigment in organic coatings. An effective strategy by combining inorganic fillers and organosilanes was used to enhance the dispersibility of silicon nitride in epoxy resin. The formed nanocomposites were applied to protect Q235 carbon steel from corrosion. The anticorrosive performance of modified silicon nitride with silane (KH-570) was investigated by electrochemical impedance spectroscopy (EIS), water absorption and pull-off adhesion methods. With the increase of immersion time, the corrosion resistance as well as adhesion strength of epoxy resin coating and unmodified silicon nitride coating decreased significantly. However, for the modified silicon nitride coating, the corrosion resistance and adhesion strength still maintained 5.7×10¹⁰ Ω cm² and 7.6 MPa after 2400-h and 1200-h immersion, respectively. The excellent corrosion resistance performance could be attributed to the chemical interactions between KH-570 functional groups and silicon nitride powders, which mainly came from the easy formation of Si-O-Si bonds. Furthermore, the modified silicon nitride coating formed a strong barrier to corrosive electrolyte due to the hydrophobic of modified silicon nitride powder and increased bonds.     

Complexities of corrosion behaviour of copper-nickel alloys under liquid impingement conditions in saline water

Flow-assisted electrochemical corrosion of Cu-Ni disc electrodes, subjected to a submerged impinging jet in saline water, was evaluated and quantified using the anodic current densities (j_a), corrosion potentials (E_corr), interfacial capacitances (C) and polarization resistances (R_p). The Reynolds numbers in the range of applied impinging velocities suggested that the flow between the solution and the electrode is turbulent in the systems investigated.The role of Ni content in the resistance of spontaneously formed barrier oxide film and diethyldithiocarbamate inhibitor film on Cu-Ni alloys (10, 20, 30 and 40 at.% Ni) was examined and evaluated using electrochemical impedance spectroscopy in dependence of the impinging velocity and the immersion time.The results are discussed in terms of the corrosion mechanisms and their relevance to the use of Cu-Ni alloys in desalination plants and in the marine engineering field because fluid hydrodynamics plays an important role in Cu-Ni alloys application. Based on the analysis presented in the paper, it is anticipated that the Cu-10Ni alloy is the best choice for application in the marine environment.     

Acetyl thiourea chitosan as an eco-friendly inhibitor for mild steel in sulphuric acid medium

Acetyl thiourea chitosan polymer (ATUCS) has been synthesized and evaluated as corrosion inhibitor. The electrochemical behavior of mild steel in naturally aerated 0.5 M H₂SO₄ acid containing different concentrations of ATUCS has been studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements and surface examination via scanning electron microscope (SEM) technique. The results of EIS showed that the resistance (R_t) increases slightly with increasing immersion time indicating a slight decrease in corrosion rate of the steel with time. Also, the corrosion rate increases with either increasing temperature or decreasing the polymer concentration as observed by polarization technique. Electrochemical impedance spectroscopy measurements under open-circuit conditions confirmed well polarization results. ATUCS has shown very good inhibition efficiency (IE) in 0.5 M sulphuric acid solution reaches to 94.5% for 0.76 mM concentration. IE of this compound has been found to vary with the concentration of the polymer solution, immersion time and temperature.     

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.     

Electrochemical and time-of-flight secondary ion mass spectrometry analysis of ultra-thin metal oxide (Al2O3 and Ta2O5) coatings deposited by atomic layer deposition on stainless steel

Ultra-thin (5–50 nm) layers of aluminium and tantalum oxides deposited by atomic layer deposition (ALD) on a stainless steel substrate (316L) for corrosion protection have been investigated by electrochemical methods (linear scan voltammetry, LSV, and electrochemical impedance spectroscopy, EIS) and time-of-flight secondary ion mass spectrometry, ToF-SIMS. The effects of the deposition temperature (250 °C and 160 °C) and coating thickness were addressed. ToF-SIMS elemental depth profiling shows a marked effect of the organic and water precursors used for deposition and of the substrate surface contamination on the level of C and OH trace contamination in the coating, and a beneficial effect of increasing the deposition temperature. The polarization data show a decrease of the current density by up to four orders of magnitude with increasing coating thickness from 5 to 50 nm. The 50 nm films block the pitting corrosion in 0.8 M NaCl. The uncoated surface fraction (quantified from the current density and allowing a ranking of the efficiency of the coating, also confirmed by the capacitance and resistance values extracted from the EIS data) was 0.03% with a 50 nm thick Al₂O₃ film deposited at 250 °C. The correlation between the porosity values of the coatings and the level of C and OH traces observed by ToF-SIMS points to a marked effect of the coating contaminants on the sealing performance of the coatings and on the corrosion resistance of the coated systems.     

Highly transparent and organosoluble polyimides derived from 2,2′‐disubstituted‐4,4′‐oxydianilines

Polypyrrole (PPy) and Polypyrrole‐ZnO (PPy‐ZnO) nanocomposites were electrodeposited on mild steel and its corrosion protection ability was studied by Tafel and Impedance techniques in 3.5% NaCl solution. Pure Polypyrrole film was not found to protect the mild steel perfectly but the coating with nano‐sized ZnO (PPy‐ZnO) has dramatically increased the corrosion resistance of mild steel. Electrochemical Impedance Spectroscopy (EIS) measurements indicated that the coating resistance (R_coat) and corrosion resistance (R_corr) values for the PPy‐ZnO nanocomposite coating was much higher than that of pure PPy coated electrode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011