Low-temperature atomic layer deposition of Al2O3 thin coatings for corrosion protection of steel: Surface and electrochemical analysis

ToF-SIMS, XPS, voltammetry and EIS investigation of the anti-corrosion properties of thin (10, 50 and 100 nm) alumina coatings grown by atomic layer deposition at 160 °C on steel is reported. Surface analysis shows a thickness-independent Al₂O₃ stoichiometry of the coating and trace contamination by the growth precursors. The buried coating/alloy interface has iron oxide formed in ambient air and/or resulting from the growth of spurious traces in the initial stages of deposition. Electrochemical analysis yields an exponential decay of the coating porosity over four orders of magnitude with increasing thickness, achieved by sealing of the more defective first deposited 10 nm.     

Evolution of dissolution processes at the interface of carbon steel corroding in a CO2 environment studied by EIS

The evolution of interfacial phenomena during CO₂ corrosion of C1018 carbon steel was characterized by EIS (Electrochemical Spectroscopy Impedance) and LPR (Linear Polarization Resistance). Turbulent conditions were simulated by a channel flow cell with deoxygenated 3 wt.% NaCl solution at 80 °C and pH 6 during 158 h. EIS helped in the characterization of the dynamic mechanism during the formation of the unprotective porous Fe₃C layer, and subsequent precipitation of the protective FeCO₃ layer inside the cementite. The experimental response of the active states at the interface was characterized by electrical passive elements with constant phase parameter analogs showing good agreement with the experimental results.     

Self-healing properties of protective coatings containing isophorone diisocyanate microcapsules on carbon steel surfaces

Microcapsules containing isophorone diisocyanate (IPDI) were used as self-healing additives in the alkyd varnish coatings (AVCs), and their self-healing performance was evaluated in the case of artificial defects on Q235 steel surfaces, using scanning micro-reference electrode technique and Fourier-transform infrared spectroscopy. Comparison of the micromechanical properties between the water-insoluble self-healing products (polyurethanes) and AVCs indicates that the former significantly enhanced the capability of the scratched crevice to successfully endure outer stress. The electrochemical impedance spectroscopy experiments analysed the different stages in the self-healing process. This study successfully demonstrated the self-healing activity of IPDI-AVCs in protecting steel surfaces.     

EIS study of the corrosion behaviour of zinc-based coatings on steel in quiescent 3% NaCl solution. Part 2: coatings covered with an inhibitor-containing lacquer

An EIS study has been made of the behaviour of several lacquered and inhibited zinc-based coatings on steel exposed to a 3% NaCl solution in quiescent conditions. Under the hypothesis that the HF-LF arc supplied the R_t value of the corrosion reaction, the possibility of obtaining quantitative information about the effect of the lacquer film and the inhibitor on the progress of attack has been demonstrated. Different values of the constant B in the Stern-Geary equation must be used depending on the specific metallic coating tested. The relatively high interfacial capacitance values of the lacquered coating suggest a highly defective lacquer film which leave a considerable fraction of the surface of the metallic substrate exposed to the corrosive medium.     

EIS study of the corrosion behaviour of zinc-based coatings on steel in quiescent 3% NaCl solution. Part 1: directly exposed coatings

The possibilities offered by the EIS technique for studying the progress of corrosion in several types of galvanised coatings were investigated. Corrosion tests were performed in a 3 wt.% NaCl aqueous solution, at approximately neutral pH, without stirring and in contact with the air. A tendency was seen towards an electrochemical overestimation of the corrosion values of essentially pure zinc and Zn-5%Al (Galfan) coatings compared with the gravimetric reference values. In contrast, the opposite tendence was revealed with the Zn-10%Fe (Galvanneal) coating. These deviations have made it necessary to use empirical values of the constant B of the Stern-Geary equation. The approximately linear progress of the attack with immersion time suggests a slight barrier effect of the corrosion products layer.     

The evaluation of coating performance by the variations of phase angles in middle and high frequency domains of EIS

Electrochemical impedance spectra (EIS) of six coating systems in 3.5% NaCl solution were measured and the relations between coating resistances and phase angles at different frequencies were analyzed. The results indicated that in middle frequency range, the phase angle and the coating resistance show similar decreasing tendencies. For the coating systems studied, the variation of phase angles at 10 Hz with immersion time was very close to the variation of coating resistance, hence may qualitatively reflect the coating performance. For the studied coating systems, the phase angle at 10 Hz decreased continuously from the beginning, indicating the permeation of the coating system by the electrolytes. When the phase angle reached a relatively stable stage, for different coating systems which was below 40°–20°, meaning the coating has been permeated through and electrochemical reactions under the coatings occurred. In addition, the phase angle at 15 kHz may reflect the state of coating in later stage. These phase angle parameters may be used as quick measurements to evaluate coating performance.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.     

Corrosion performance of epoxy coatings containing silane treated ZrO2 nanoparticles on mild steel in 3.5% NaCl solution

Clear epoxy coatings were modified by adding various levels of ZrO₂ nanoparticles. In order to achieve proper dispersion of nanoparticles in the epoxy-based coating and making possible chemical interactions between nanoparticles and polymeric coating, the surface of the nanoparticles was treated with amino propyl trimethoxy silane (APS). Corrosion performance of mild steel coated specimens was investigated employing EIS, electrochemical noise (ECN) techniques and salt spray test. Coatings with 2–3 wt% ZrO₂ nanoparticles possessed the best corrosion performance among the coating specimens. Possible chemical interactions between polymeric matrix and treated nanoparticles in nanocomposites cause high barrier properties and ionic resistances.     

EIS study on degradation of polymer-coated steel under ultraviolet radiation

Degradation of heavy-duty steel coatings when exposed to ultraviolet (UV) radiation was investigated by electrochemical impedance spectroscopy (EIS) and additional techniques in order to clarify the feasibility of evaluation of the UV degradation by EIS. Two coatings were considered: polyester-urethane topcoat plus epoxy primer (PU/E) and epoxy topcoat plus epoxy primer (E/E). Each was applied to a steel substrate and exposed to cyclic wetting-drying under UV radiation. The PU/E coating developed topcoat cracks but did not delaminate from the substrate; capacitive behaviour was evident, and corrosion of the underlying steel was not observed. The E/E coating showed topcoat chalking and partial disappearance, exposing the primer, but corrosion of the underlying steel was not observed. The morphology and chemical changes were compared with the results of EIS.     

Inhibitors performance in CO2 corrosion: EIS studies on the interaction between their molecular structure and steel microstructure

The performance of three imidazoline-like inhibitors in CO₂ corrosion was studied by means of electrochemical measurements employing a.c. and d.c. techniques. Carbon steel with two different microstructures (annealed, and quenched and tempered (Q&T)) was used in a deoxygenated 5% wt. NaCl solution, saturated with CO₂ at 40 °C and pH 6. Aminopropylimidazol (API) and two commercial imidazoline-based products (PC and QB) were used as inhibitors. Electrochemical impedance spectroscopy (EIS) and linear polarization resistance (LRP) studies showed that the annealed samples have a better corrosion resistance than the Q&T samples when API and PC were added. On the other hand, the presence of QB yielded the opposite results. From the Bode phase angle plots it can be concluded that in the first case and for both microstructural conditions, there is no indication of formation of an inhibitor film, whereas in the presence of QB its formation is clearly evident. Based on these experimental findings, a mechanism of action for each inhibitor is proposed.     

Kinetics of H2O2 reaction with oxide films on carbon steel

The nature of carbon steel surfaces in 0.01 M borate solutions (pH 10.6) have been characterized using a range of electrochemical techniques and ex situ analyses such as Raman and Auger spectroscopy. Their subsequent behaviour on exposure to 10⁻³ M H₂O₂-containing solutions has also been studied. The anodically oxidized carbon steel surfaces have been characterized according to three regions: (I) the potential range <−0.5 V (vs SCE), when the surface is active and covered by Fe^II/Fe^III oxide/hydroxide; (II) the potential range −0.5 V to 0.0 V when the surface is passivated by an outer layer of Fe^III oxide/hydroxide over the inner layer of Fe^II/Fe^III oxide/hydroxide; and (III) potentials >0 V when further growth of the underlying layer appears to lead to minor film breakdown/restructuring. The addition of H₂O₂ to films grown in the passive region or above (II and III) leads initially to a degradation of the outer layer allowing increased growth of the inner layer. Subsequently, the outer passivating layer is repaired and passivity re-established. These changes appear to be confirmed by Raman spectroscopy.     

The effect of electrolyte flow on the performance of 12-aminododecanoic acid as a carbon steel corrosion inhibitor in CO2-saturated hydrochloric acid

The effect of flow and flow pattern of CO₂-saturated HCl on the corrosion inhibition of carbon steel (CS) by 12-aminododecanoic acid (AA) was investigated in a square duct, rotating disk electrode (RDE), and jet impingement cell configuration. 3 mM AA provided high corrosion inhibition efficiency in the square duct and RDE configuration. However, in 1 mM AA the inhibition efficiency decreased with an increase in Re, due to desorption of AA from the CS surface. AA was found to poorly protect CS in the impingement-jet configuration at low Re, while at high Re, acceleration of CS corrosion was recorded.     

Painting rusted steel: The role of aluminum phosphosilicate

Surface preparation is a key factor for the adequate performance of a paint system. The aim of this investigation is to employ a wash-primer to accomplish the chemical conversion of rusted surface when current cleaning operations are difficult to carry out. The active component of the wash-primer was aluminum phosphosilicate whose electrochemical behavior and the composition of the generated protective layer, both, were studied by electrochemical techniques and scanning electron microscopy (SEM), respectively. Primed rusted steel panels were coated with an alkyd system to perform accelerated tests in the salt spray chamber and electrochemical impedance measurements (EIS). These tests were conducted in parallel with a chromate wash primer and the same alkyd system. Results showed that the wash-primer containing aluminum phosphosilicate could be used satisfactorily to paint rusted steel exhibiting a similar performance to the chromate primer.     

Corrosion inhibition of carbon steel in tetra-n-butylammonium bromide aqueous solution by benzotriazole and Na3PO4

The corrosion inhibition behavior of benzotriazole, Na₃PO₄ and their mixture on carbon steel in 20 wt.% (0.628 mol l⁻¹) tetra-n-butylammonium bromide aerated aqueous solution was investigated by weight-loss test, potentiodynamic polarization measurement, electrochemical impedance spectroscopy and scanning electron microscope/energy dispersive X-ray techniques. The inhibition action of BTA or SP or inhibitors mixture on the corrosion of carbon steel is mainly due to the inhibition of anodic process of corrosion. The results revealed that inhibitors mixtures have shown synergistic effects at lower concentration of inhibitors. At 2 g l⁻¹ BTA and 2 g l⁻¹ SP showed optimum enhanced inhibition compared with their individual effects.     

Influence of various surface treated silica nanoparticles on the electrochemical properties of SiO2/polyurethane nanocoatings

Various organosilane-treated SiO₂ nanoparticles were dispersed in a 2-pack polyurethane coating. The influence of surface modification and silica content on the electrochemical behaviour of the resultant nanocoatings was investigated. Electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) variations were examined. The surface chemistry of nanoparticles and its effect on the resultant nanocoating morphology were also studied utilising FTIR, and TEM analyses. The results reveal that the presence of more hydrophobic groups and longer-lengthed hydrophobic chains on the surface of nanoparticles, greatly improves the interfacial interactions at the polymer/filler interfaces resulting in a better corrosion performance.     

Corrosion of N80 carbon steel in oil field formation water containing CO2 in the absence and presence of acetic acid

Corrosion behaviour of N80 carbon steel in formation water containing CO₂ was studied by polarization curve technique, electrochemical impedance spectroscopy, weight loss test, scanning electron microscope, and X-ray diffraction. Effects of temperature and acetic acid concentration on the corrosion behaviour of N80 carbon steel were discussed. The results showed that increasing temperature not only enhanced the dissolution of steel substrate, but also promoted the precipitation of FeCO₃, the addition of acetic acid enhanced localized corrosion attack on N80 carbon steel. FeCO₃ was the main corrosion product. And there was a transition region between CO₂ corrosion control and HAc corrosion control.     

Synergism between red tetrazolium and uracil on the corrosion of cold rolled steel in H2SO4 solution

The synergism between red tetrazolium (RT) and uracil (Ur) on the corrosion of cold rolled steel (CRS) in H₂SO₄ solution is first investigated by weight loss, potentiodynamic polarization, and atomic force microscope (AFM). Effects of inhibitor concentration (25-500 mg l⁻¹), temperature (20-50 °C), and acid concentration (1.0-5.0 M) on synergism are discussed systematically. The results reveal that RT has a moderate inhibitive effect, and its adsorption obeys the Freundlich adsorption isotherm. For Ur, it has a poor effect. However, incorporation of RT with Ur significantly improves the inhibition performance, and produces synergistic inhibition effect.     

Effect of sintering temperature on corrosion properties of sol–gel based Al2O3 coatings on pre-treated AZ91D magnesium alloy

A novel anti-corrosion sol–gel based Al₂O₃ coating was developed on the AZ91D magnesium alloy. The morphology, microstructure and composition of the coatings were investigated by scanning electron microscope coupled with energy dispersive spectroscopy, Fourier transform infrared spectrum analysis, X-ray diffraction, thermo-gravimetric and differential thermal analysis. The corrosion resistance of the coatings in 3.5 NaCl wt.% solution was studied using electrochemical measurements. The results demonstrated that a homogeneous Al₂O₃ coating could be obtained and the sol–gel coated samples sintered at 380 °C had the best corrosion resistance properties as compared to the specimens sintered at 120 and 280 °C.     

Synergistic inhibition effect of 6-benzylaminopurine and iodide ion on the corrosion of cold rolled steel in H3PO4 solution

The synergistic inhibition effect of 6-benzylaminopurine (BAP) and iodide ion (I⁻) on the corrosion of cold rolled steel (CRS) in 1.0 M H₃PO₄ solution was studied by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results show that BAP has a moderate inhibitive effect. However, incorporation of BAP with I⁻ improves the inhibition performance significantly. The adsorption of BAP in the absence and presence of I⁻ obeys Langmuir adsorption isotherm. BAP and BAP/I⁻ mixture act as mixed-type inhibitors. A probable synergism mechanism is proposed.     

Synergistic inhibition behaviour of methylbenzyl quaternary imidazoline derivative and iodide ions on mild steel in H2SO4 solutions

The inhibition behaviour of 2-undecyl-1-ethylamino-1-methylbenzyl quaternary imidazoline (2UMQI) and KI on mild steel in 1.0 M H₂SO₄ solutions was investigated at 25 °C using electrochemical methods. The results indicated that 2UMQI inhibited the corrosion of mild steel and the extent of inhibition increased with 2UMQI concentrations. The inhibition action in the presence of 2UMQI is due to physical adsorption of 2UMQI. A mixed-inhibition mechanism is proposed for the inhibitive effects of 2UMQI. Inhibition efficiency of 2UMQI was enhanced by the addition of iodide ions. In the presence of KI, the potentials of unpolarization, E_u was observed and increased with KI concentration.