Electrochemical anticorrosion performance evaluation of Al2O3 coatings deposited by MOCVD on an industrial brass substrate

Alumina (Al₂O₃) coatings of different thickness were deposited on OT59 brass substrate (BS) using the metal organic chemical vapour deposition (MOCVD) technique to evaluate the corrosion performance by EIS measurements. The used precursor was dimethyl-aluminium-isopropoxide. Electrochemical characterizations of the deposited films were performed in a standard very aggressive acidic solution (aerated 1N H₂SO₄ at 25 °C up to 168 h of immersion time) by means of direct current method (Tafel curves) and electrochemical impedance spectroscopy (EIS). The Rutherford backscattering spectroscopy (RBS) indicated that the films are very pure with the correct Al₂O₃ stoichiometry, while the IR absorption spectra showed that the films did not contain any OH groups. The surface film morphology was investigated by atomic force microscopy (AFM) and displayed a globular texture. The films were very smooth, with a maximum root mean square roughness, for example, of 14 nm for a 0.96 μm thick coating. The EIS data confirmed, as expected, that a 2.40 μm Al₂O₃ layer ensures the best corrosion protection after 168 h of immersion in the very acidic environment used.     

Protective ability of hybrid nano-composite coatings with cerium sulphate as inhibitor against corrosion of AA2024 aluminium alloy

The corrosion protective ability of hybrid oxy silane nano-composite coatings deposited on AA2024 by sol-gel technique was studied. The coatings are developed as an environmentally friendly alternative of the toxic chromium containing coatings on aluminium. A cerium salt, Ce₂(SO₄)₃, was used as inhibitor of the corrosion process. Two methods were applied to introduce the salt in the hybrid matrix: directly in the matrix, or by porous Al₂O₃ nano-particles preliminary loaded by the salt. Atomic force microscopy (AFM) was used to evaluate the superficial morphology of the coatings, while their layer structure was studied by means of scanning electron microscopy (SEM). Linear voltammetry (LVA) and electrochemical impedance spectroscopy (EIS) were used for assessment of the barrier ability. The hybrid matrix was found to possess remarkable barrier ability which was preserved even after prolonged exposure of the coatings to a model corrosive medium of 0.05 M NaCl. In all cases, the cerium salt involved either directly or by Al₂O₃ nano-particles proved to deteriorate the protective properties of the coatings and to accelerate pitting nucleation. The experimental results have shown that cerium sulphate, introduced in the by the both manners in the hybrid matrix did not efficiently inhibit the corrosion of AA2024, unlike the reported inhibiting properties of other cerium salts.     

Nanostructured sol-gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3: Corrosion protection performance

Nanostructured hybrid sol-gel coatings doped with cerium ions were investigated in the present work as pre-treatments for the AA2024-T3 alloy. The sol-gel films have been synthesized from tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) precursors. Additionally the hybrid sol was doped with zirconia nanoparticles prepared from hydrolyzed tetra-n-propoxyzirconium (TPOZ). Cerium nitrate, as corrosion inhibitor, was added into the hybrid matrix or into the oxide nanoparticles.The chemical composition and the structure of the hybrid sol-gel films were studied by XPS (X-ray photoelectron spectroscopy) and AFM (atomic force microscopy), respectively. The evolution of the corrosion protection properties of the sol-gel films was studied by EIS (electrochemical impedance spectroscopy), which can provide quantitative information on the role of the different pre-treatments. Different equivalent circuits, for different stages of the corrosion processes, were used in order to model the coating degradation. The models were supported by SEM (scanning electron microscopy) measurements.The results show that the sol-gel films containing zirconia nanoparticles present improved barrier properties. Doping the hybrid nanostructured sol-gel coatings with cerium nitrate leads to additional improvement of the corrosion protection. The zirconia particles present in the sol-gel matrix seem to act as nanoreservoirs providing a prolonged release of cerium ions. The nanostructured sol-gel films doped with cerium nitrate can be proposed as a potential candidate for substitution of the chromate pre-treatments for AA2024-T3.     

Poly(N-ethylaniline) coatings on 304 stainless steel for corrosion protection in aqueous HCl and NaCl solutions

Poly(N-ethylaniline) (PNEA) coatings were grown by potentiodynamic synthesis technique on 304 stainless steel (SS) alloy from 0.1 M of N-ethylaniline (NEA) in 0.3 M oxalic acid solution. Characterization of adhesive and electroactive PNEA coatings was carried out by cyclic voltammetry, FT-IR spectroscopy and scanning electron microscopy (SEM) techniques. The protective properties of PNEA coatings on SS were elucidated using linear anodic potentiodynamic polarization, Tafel and electrochemical impedance spectroscopy (EIS) test techniques, in highly aggressive 0.5 M HCl and 0.5 M NaCl solutions. Linear anodic potentiodynamic polarization test results proved that PNEA coating improved the degree of protection against pitting corrosion in HCl and NaCl solutions. Tafel test results showed that PNEA coating appears to enhancement protection for SS in 0.5 M NaCl and 0.5 M HCl solutions. However, according to long-term EIS results, PNEA coating is better for the protection of SS electrodes during the long immersion period in NaCl compared to that in HCl medium.     

Enhanced corrosion resistance of A3xx.x/SiCp composites in chloride media by La surface treatments

The influence of silicon carbide particles (SiCp) proportion and matrix composition of aluminium metal matrix composites (A3xx.x/SiCp) modified by lanthanum-based conversion or electrolysis coating was evaluated in 3.5 wt% NaCl aerated solution. The intermetallic compounds were preferentially covered by lanthanum-based conversion coatings obtained by immersion in 50 °C solution of La(III) salt, and the intermetallic compounds, SiCp and aluminium matrix were covered by lanthanum electrolysis treatment. The corrosion process was studied on the basis of gravimetric tests and electrochemical impedance spectroscopy (EIS) during immersion in 3.5 wt% NaCl aerated solution. The composition of both La coating and corrosion products was analyzed before and after accelerated testing, by scanning electron microscopy (SEM), atomic force microscopy (AFM), low-angle X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) to determine the influence of surface microstructural changes on corrosion behaviour during exposure to the corrosive environment. The corrosion process was more influenced by the concentration of alloy elements in the matrix than by the proportion of SiCp reinforcement. Both lanthanum treated surfaces presented better behaviour to chloride solution corrosion than original composite surfaces without treatment; however, electrolysis afforded a higher degree of protection than the conversion treatment because the coating was more extensive.     

硅溶胶对无机磷酸铝涂料防腐性能的影响

采用化学合成法制备磷酸铝粘结剂,以球形铝粉为骨料,添加不同含量的硅溶胶,制备磷酸铝涂料,再经过热处理制备磷酸铝涂层。通过X射线衍射分析(XRD)表征粘结剂和涂层物相结构,采用扫描电子显微镜(SEM)表征涂层形貌,通过电化学测试和浸泡试验对比研究涂层腐蚀行为。分析结果表明:在磷酸铝涂层中添加适量硅溶胶可以改善涂层表面质量和耐腐蚀性能,从而使涂层腐蚀电位升高,腐蚀电流降低,阻抗值增大。添加10%硅溶胶的涂层质量最佳,耐腐蚀性能最优。     

Effect of cerium concentration on microstructure,morphology and corrosion resistance of cerium–silica hybrid coatings on magnesium alloy AZ91D

The aim of this work was to investigate the effect of cerium concentration on microstructure, morphology and anticorrosion performance of cerium–silica hybrid coatings on magnesium alloy AZ91D. Vinyltriethoxysilane (VETO) and γ-glycidoxypropyltrimethoxysilane (GPTMS) were employed as precursors to prepare sol–gel based silica coating. Cerium nitrate hexahydrate as dopant in five different concentrations was added into the silica coatings. Fourier transform infrared (FT-IR) spectrum analysis, viscosity measurements and scanning electron microscopy (SEM) were employed to characterize the microstructure and morphology of these coatings. It was found that with the increase of cerium concentration, the degree of decomposition of silane chains in the coating network increased. The corrosion resistance of the cerium–silica hybrid coatings was estimated by electrochemical impedance spectroscopy (EIS) measurements and potentiodynamic polarization tests. The results demonstrated that corrosion resistance of coatings initially increases and then decreases as cerium concentration goes up. When the cerium concentration is 0.01 M, corrosion resistance reaches its maximum.     

Electropolymerization, characterization and corrosion performance of poly(N-ethylaniline) on copper

Poly(N-ethylaniline) (PNEA) coatings were grown by cyclic voltammetry technique on copper from 0.1 M N-ethylaniline (NEA) in 0.3 M oxalic acid solution. The optimum conditions (e.g. upper potential limit, scan rate and cycle number) effect on corrosion performance of synthesized PNEA films were determined in order to obtain best protection results against corrosion. The electrodeposited coatings were characterized by cyclic voltammetry (CV), Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) spectroscopy and scanning electron microscopy (SEM). Redox parameters were found after electrochemical tests and results of stability tests of these films impart an electroactive behavior that is composed of both diffusion control and thin film behavior. In addition, corrosion performance of PNEA coatings were investigated in 0.1 M H₂SO₄ by Tafel extrapolation and electrochemical impedance spectroscopy (EIS) techniques.     

Evidence of Electrochemical Resistance on Ternary V-C-N Layers

In this research, vanadium carbo-nitride (VCN) coatings were synthesized via physical vapor deposition with the aim to determinate the electrochemical behavior of the VCN layers on industrial steel substrates. The VCN coatings, deposited at various negative bias voltage were characterized by X-ray diffraction (XRD), exhibiting the crystallography orientations corresponding to a mix of VCN, VC and VN phases while the X-ray photoelectron spectroscopy (XPS) measurements were used to determinate the chemical composition of the metallic carbon-nitride materials. By using electrochemical impedance spectroscopy (EIS) and Tafel curves, it was possible to estimate the electrochemical behavior of the VCN coatings in a sodium chloride (NaCl) solution. Moreover, scanning electron microscopy (SEM) was performed to analyze morphological and chemical surfaces changes on the VCN layer due to the reaction in NaCl/VCN/steel surface interface. The electrochemical behavior of the VCN coatings in relation to the uncoated AISI 8620 steel showed a reduction of 98% in the corrosion rate, indicating that the applied VCN coatings may be a promising material for industrial applications.     

Self-assembled 1-octadecyl-1H-1,2,4-triazole films on copper for corrosion protection

A film of 1-octadecyl-1H-1,2,4-triazole (OTA) was formed on a fresh copper surface by self-assembly technique. The optimum concentration of OTA and immersion time for the formation of a protective OTA film have been established using electrochemical impedance spectroscopy (EIS). These are (i) 15 mM concentration of OTA in methanol and (ii) immersion period of 48 h. X-ray photoelectron spectroscopy (XPS), reflection absorption FTIR spectroscopy, atomic force microscopy (AFM), and contact angle measurements have been used to characterize the OTA film on copper surface. The efficiency of OTA film to protect copper from corrosion in aqueous NaCl environment has been investigated using EIS, potentiodynamic polarization studies, cyclic voltammetry and weight-loss studies. All these studies showed that the OTA film affords excellent protection against corrosion of copper.     

Enhancement of corrosion protection of mild steel by chitosan/ZnO nanoparticle composite membranes

The development of active corrosion protection systems for metallic substrates is an issue of prime importance for many industrial applications. Nanostructured chitosan/ZnO nanoparticle films were coated on mild steel by sol–gel process, dip coating technique. Sol–gel protective coatings have shown excellent chemical stability, oxidation control and enhanced corrosion resistance for metal substrates. Further, the sol–gel method is an environmentally friendly technique of surface protection which has traditionally been used for increasing corrosion resistance of metals. Films so formed were characterized by UV–vis absorption spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray fluorescence spectrometry (EDX). Corrosion protection behavior of these coated mild steel substrates in 0.1 N HCl solutions was evaluated by potentiodynamic polarisation studies (Tafel), linear polarisation studies (LPR), electrochemical impedance spectroscopy studies (EIS).     

Electrodeposited Ni-B alloy coatings: Structure, corrosion resistance and mechanical properties

Ni-B alloy coatings with different boron content ranging from 4 to approximately 28 at.% were prepared by electrodeposition in a nickel-plating bath containing sodium decahydroclovodecaborate as a boron source. The influence of the boron concentration in the coatings on their structure, morphology, electrochemical and corrosion behavior, physico-mechanical and electrical properties was investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and other methods. It was found that the electrodeposited Ni-B coatings with relatively low boron content (≤8 at.%) are nanocrystalline and comprise a solid solution of boron in f.c.c. Ni lattice having a mixed substituted-interstitial type. Further increase in the boron content (up to 10-15 at.%) leads to the appearance of heterogeneous amorphous-nanocrystalline structure, and the coatings with a high boron content (20 at.% and above) are X-ray amorphous. Polarization measurements in neutral NaCl solutions showed that the Ni-B coatings with relatively low boron content demonstrate a potential region of low anodic currents associated with the passive film formation at the alloy surface. The anodic current in this potential region increases significantly with increasing the boron content above 10 at.%, suggesting the non-protective nature of the anodic film formed on the amorphous Ni-B alloys. Immersion tests monitored by EIS measurements revealed a significantly better corrosion performance of the Ni-B coatings with low boron content (4 at.%) in comparison with that of the amorphous coatings. The microhardness and wear resistance of the Ni-B coatings essentially increases with increasing the boron content. Maximum microhardness and wear resistance were found for the coatings containing 8 at.% B.     

Effect of saccharin addition on the corrosion resistance of polypyrrole coatings

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

Self-healing and anticorrosive properties of Ce(III)/Ce(IV) in nanoclay–epoxy coatings

The self-healing and anticorrosion effects of cerium nitrate in epoxy–clay nanocomposite coatings systems were studied. Different amounts of cerium (III) were added to epoxy–montmorillonite clay composites and the nanocomposite coatings were prepared and applied on cold rolled steel panels. Ultrasonication was applied to disperse the nanoclay into the epoxy cerium nitrate composition. Electrochemical impedance spectroscopy (EIS) was used to study the self-healing and anticorrosion behaviors of the coatings. The structure of the dry coating and the protective mechanism of the pigments in the coating were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) analysis and field emission electron microscopy (FESEM). Transmission electron microscopy (TEM) illustrated the separation of clay layers which interacted with the epoxy resin. Electrochemical impedance data indicated that the epoxy cerium (III)–montmorillonite nanocomposite coatings were superior to the epoxy coatings in corrosion protection properties. The self-healing behavior of such coatings was due to the presence of cerium nitrate that could be released at the defects within the coating and hindered the corrosion reactions at the defective sites. It was shown that the best corrosion protection was achieved with nanocomposite coatings containing 4 wt% clay and 2 wt% cerium nitrate.     

Studying the corrosion protection properties of an epoxy coating containing different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments

Epoxy/polyamide coatings were loaded with different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments. Moreover, a coating containing zinc phosphate (ZP) was prepared as a reference sample. The coatings were applied on St-37 steel substrates and then were exposed to 3.5 wt% NaCl solution up to 35 days. The corrosion inhibition properties of the pigments extracts were studied on bare steel samples by a potentiodynamic polarization technique after 24 h immersion. The morphological properties and corrosion resistance of the coatings were investigated by scanning electron microscope (SEM), optical microscope, electrochemical impedance spectroscopy (EIS) and salt spray tests.     

Effect of Al and Ag dopants on the corrosion resistance of the AISI 316L-YSZ system

We present results for the deposition of coatings of zirconium stabilized with Yttria (YSZ) and doped with aluminum and silver. The coatings were grown from an YSZ ceramic target symmetrically covered with metallic (Al, Ag) pieces on AISI 316L steel substrates, via the RF sputtering technique. The microstructure of the coatings was characterized by means of X-ray diffraction (XRD), the chemical composition was determined through X-ray dispersive energy (EDX) analysis, and the electrochemical response was evaluated via impedance (EIS) and Tafel corrosion techniques. The XRD analysis showed that the coatings exhibited peaks belonging to the target material, dopant elements, and oxides such as Al₂O₃. Electrochemical analysis indicated an increase in the corrosion resistance of the coatings grown on aluminum oxide.     

Characterization of structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings prepared through an ultrasonication assisted process

In this study, a series of castor oil based polyurethane/organically modified montmorillonite (OMMT) clay nanocomposite coatings have been successfully prepared by effective dispersing of OMMT nano-layers in polyurethane matrix through an ultrasonication assisted process. Effectiveness of ultrasonication process in de-agglomeration of clay stacks in castor oil dispersions was evaluated by optical microscopy and sedimentation test. Structure of nanocomposite coatings was investigated by wide angle X-ray diffraction (WAXD) and Fourier-transform infrared spectroscopy (FT-IR). The anticorrosive properties of nanocomposite coatings were characterized by electrochemical impedance spectroscopy (EIS), Tafel polarization study, water absorption and pull-off adhesion tests. The experimental results showed that PU/OMMT nanocomposite coatings were superior to the neat PU in corrosion protection effects. Also, it was observed that the corrosion protection of polyurethane organoclay nanocomposite coatings is improved as the clay loading is increased up to 3 wt.%.     

Electrochemical stability and surface analysis of a new alkyd paint with low content of volatile organic compounds

This paper presents the results regarding the electrochemical stability and surface analysis of a new alkyd paint with low content of volatile organic compounds in comparison with a conventional alkyd paint. The alkyd films were realized on carbon steel substrate. Dry films thickness in 30–35 μm range was obtained. The experimental tests were carried out in 3% NaCl solution at the 25 °C temperature. The electrochemical techniques (electrochemical impedance spectroscopy (EIS), potentiodynamic and Tafel polarization) and surface analysis techniques (AFM, SEM, EDX) were used to evaluate protective properties of the tested paint films. The correlation of all experimental results established that the new alkyd paint with low content of volatile organic compounds presents better protective performances and lower permeability than conventional alkyd paint. AFM, SEM and EDX indicated a compact, homogenous, non-porous and adherent coating.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Effect of ethylenediamine tetraacetic acid disodium on the corrosion of cold rolled steel in the presence of benzotriazole in hydrochloric acid

The inhibition behavior of cold rolled steel in 0.1 M hydrochloric acid (HCl) by ethylenediamine tetraacetic acid disodium (EDTA) in the absence and presence of benzotriazole (BTA) was investigated with Tafel polarization curve and electrochemical impedance spectroscopy (EIS). The polarization curve results show that the single EDTA acts as an anodic type inhibitor while the combination of EDTA and BTA acts as mixed type inhibitor and mainly inhibits anodic reaction. All impedance spectra in EIS tests exhibit one capacitive loop which indicates that the corrosion reaction is controlled by charge transfer process. Inhibition efficiencies obtained from Tafel polarization, charge transfer resistance (R_t) are consistent. The corrosion of cold rolled steel in 0.1 M HCl is obviously reduced by EDTA in combination with lower concentrations of BTA. Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) were used to characterize the corrosion surface of cold rolled steel. Probable mechanisms are present to explain the experimental results.