Electrochemical corrosion behaviour of plasma electrolytic oxidation coatings on AM50 magnesium alloy formed in silicate and phosphate based electrolytes

PEO coatings were produced on AM50 magnesium alloy by plasma electrolytic oxidation process in silicate and phosphate based electrolytes using a pulsed DC power source. The microstructure and composition of the PEO coatings were analyzed by scanning electron microscopy (SEM) and X-ray Diffraction (XRD). The corrosion resistance of the PEO coatings was evaluated using open circuit potential (OCP) measurements, potentiodynamic polarisation tests and electrochemical impedance spectroscopy (EIS) in 0.1 M NaCl solution. It was found that the electrolyte composition has a significant effect on the coating evolution and on the resulting coating characteristics, such as microstructure, composition, coating thickness, roughness and thus on the corrosion behaviour. The corrosion resistance of the PEO coating formed in silicate electrolyte was found to be superior to that formed in phosphate electrolyte in both the short-term and long-term electrochemical corrosion tests.     

Influence of chloride ion concentration on the electrochemical corrosion behaviour of plasma electrolytic oxidation coated AM50 magnesium alloy

The electrochemical degradation of a silicate- and a phosphate-based plasma electrolytic oxidation (PEO) coated AM50 magnesium alloy obtained using a pulsed DC power supply was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in NaCl solutions of different chloride ion concentrations viz., 0.01 M, 0.1 M, 0.5 M and 1 M. The surface of the PEO coated specimens after 50 h of immersion/EIS testing was examined by optical microscopy and scanning electron microscopy. The results showed that the corrosion deterioration of PEO coated magnesium alloy in NaCl solutions was significantly influenced by chloride ion concentration. The silicate-based coating was found to offer a superior corrosion resistance to the magnesium substrate than the phosphate-based coatings in lower chloride ion concentration NaCl solutions (0.01 M and 0.1 M NaCl). On the other hand both these PEO coatings were found to be highly susceptible to localized damage, and could not provide an effective corrosion protection to Mg alloy substrate in solutions containing higher chloride concentrations (0.5 M and 1 M). The extent of localized damage was observed to be more with increase in chloride concentration in both the cases.     

Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy

This work aims to develop and study new anticorrosion films for AZ31B magnesium alloy based on the sol-gel coating approach.Hybrid organic-inorganic sols were synthesized by copolymerization of epoxy-siloxane and titanium or zirconium alkoxides. Tris(trimethylsilyl) phosphate was also used as additive to confer additional corrosion protection to magnesium-based alloy. A sol-gel coating, about 5-μm thick, shows good adhesion to the metal substrate and prevents corrosion attack in 0.005 M NaCl solution for 2 weeks. The sol-gel coating system doped with tris(trimethylsilyl)-phosphate revealed improved corrosion protection of the magnesium alloy due to formation of hydrolytically stable Mg-O-P chemical bonds.The structure and the thickness of the sol-gel film were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The corrosion behaviour of AZ31B substrates pre-treated with the sol-gel derived hybrid coatings was tested by electrochemical impedance spectroscopy (EIS). The chemical composition of the silylphosphate-containing sol-gel film at different depths was investigated by X-ray photoelectron spectroscopy (XPS) with depth profiling.     

Preparation and corrosion resistance studies of nanometric sol-gel-based CeO2 film with a chromium-free pretreatment on AZ91D magnesium alloy

Magnesium alloy, although valuable, is reactive and requires protection before it can be applied in many fields. In this study, a novel protective environmental-friendly gradient coating was performed on AZ91D magnesium alloy by non-chromate surface treatments, which consisted of phytic acid chemical conversion coating and the sol-gel-based CeO₂ thin film. The surface morphologies, microstructure and composition of the coatings were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. The effects of the concentration, layers, temperature of heat treatment of CeO₂ sol on the anti-corrosion properties of the gradient coating for magnesium were also investigated. The results showed that the gradient coating was mainly composed of crystalline CeO₂. According to the results of electrochemical tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this new environmental-friendly surface treatment.     

Structure and electrochemical characterization of electrolytic Ni + Mo + Si composite coatings in an alkaline solution

Ni + Mo + Si coatings were obtained by nickel deposition from a bath containing suspension of molybdenum and silicon powders. These coatings were obtained in galvanostatic conditions, at the current density of j_dep = −0.100 A cm⁻². For determination of the influence of phase composition and surface morphology of obtained coatings on changes of corrosion resistance, these coatings were modified in argon atmosphere by thermal treatment at the temperature of 1100 °C during 1 h. A scanning electron microscope was used for surface morphology characterization of the coatings. Chemical composition of obtained coatings was determined by X-ray fluorescence spectroscopy method. Phase composition investigations were conducted by X-ray diffraction method. It was found that the obtained coatings are composed of three phase structures, i.e., nickel, molybdenum and silicon. Phase composition for the Ni + Mo + Si coatings after thermal treatment is markedly different. The main peaks corresponding to the Ni and Mo coexist with the new ones corresponding to new phases: Mo₅Si₃, NiSi, Mo₂Ni₃Si and Ni₆Mo₆C_1.06.Electrochemical corrosion resistance investigations were carried out in the 5 M KOH, using potentiodynamic and electrochemical impedance spectroscopy methods. On the basis of these investigations it was found that Ni + Mo + Si coatings after thermal treatment are more resistant in alkaline solution than Ni + Mo + Si as-deposited coatings. The reason of this is presence of silicides in the coatings.     

Styrene butadiene co-polymer based conducting polymer composite as an effective corrosion protective coating

Electroactive conducting polymer composite coatings of polyaniline (PANI) are electrosynthesized on styrene–butadiene rubber (SBR) coated stainless steel electrode by potentiostatic method using aqueous H₂SO₄ as supporting electrolyte. The protective behaviour of these coatings in different corrosion media (3.5% NaCl and 0.5 M HCl) is investigated using Tafel polarization curves, open circuit potential measurements and electrochemical impedance spectroscopy. The results reveal that SBR/PANI composite coating is much better in corrosion protection than simple PANI coating. The corrosion potential of composite films shifts to more noble values indicating that SBR/PANI composite coating act as an effective corrosion protective layer.     

A novel approach to heal the sol-gel coating system on magnesium alloy for corrosion protection

Sol-gel-based coatings exhibit high potentiality to be as an alternative to toxic chromate coatings for surface pre-treatment of metals and alloys. However, as soon as even small defects appear in the coating, the coating cannot stop the development of corrosion process. Present work demonstrates the possibility to use zinc nitrate as healing agent to repair the organic silane coatings in NaCl solution. The zinc nitrate was added to the 0.005 M NaCl solution where AZ91D magnesium alloy coated with organic silane coating was immersed. The healing process and the healing mechanism were investigated by electrochemical measurements and scanning electron microcopy coupled with energy dispersive spectroscopy. The results demonstrated the introduction of zinc nitrate to the electrolyte could stop the development of corrosion process of the coating system and a remarkable recovery on corrosion resistance could be obtained. This effect may be attributed to the formation of zinc oxide/hydroxide on the defective areas, hindering the corrosion activities.     

Multifunctional,environmental coatings on AA2024 by combining anodization with sol-gel process

The present work proposes the development of multifunctional composite coatings on AA 2024 by combining anodization and sol-gel process. To render the surface of AA 2024 with maximum corrosion resistance, eco-friendly citric-sulfuric acid (CSA) electrolyte with low sulphur content was used for anodization at 20 V for a duration of 30 min. The obtained anodized layer was porous. Ambient curable hybrid sol-gel coating with 8-hydroxy quinoline (8-HQ) as corrosion inhibitor was used as a sealant for the porous anodized layer to enhance the corrosion resistance with self-healing properties. Surface pre-treatments were carried out using sand blasting and alkaline etching to ensure high surface activity prior to anodization. The surface morphology and chemical composition of samples with and without coatings were characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectroscopic analysis (EDX). Adhesion strength and wettability of the coatings were measured by tape adhesion test and water contact angle analysis respectively, which revealed excellent binding strength and hydrophobic nature. The corrosion resistance of the coatings was evaluated using electrochemical impedance spectroscopic (EIS), potentiodynamic polarization and salt spray tests. The results revealed improved corrosion resistance of anodized + 8-HQ sealed AA2024. Moreover, when the coated samples were scribed and exposed to the corrosive medium, the SEM/EDX mapping confirmed presence of corrosion inhibitors at the location of the defect, thereby confirming the self-healing property. Hence, the proposed system is a chromium-free, environment friendly multifunctional system exhibiting excellent self-healing corrosion protection and can be a promising substitute for chromic acid anodization.     

Preparation and characterization of oxide films containing crystalline TiO2 on magnesium alloy by plasma electrolytic oxidation

Oxide films have been produced on AM60B magnesium alloy using plasma electrolytic oxidation process in an alkaline phosphate electrolyte with and without addition of titania sol. The microstructure and composition of the oxide films were analyzed by Scanning Electron Microscope (SEM), X-ray Photoelectron Spectroscope (XPS) and X-ray Diffraction (XRD). The corrosion resistances of the oxide films were evaluated using potentiodynamic polarization measurements in 3.5 wt% NaCl solution. It is found that the oxide film containing crystalline rutile and anatase TiO₂ compounds are produced in an alkaline phosphate electrolyte with addition of titania sol. The oxide film formed in electrolyte with addition of titania sol has more uniform morphology with less structural imperfections than that formed in electrolyte without addition of titania sol. The results of potentiodynamic polarization analysis show that the oxide film formed in the present modified electrolyte is successful in providing superior corrosion resistance for magnesium alloy.     

Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy

This work investigates the protective behaviour of bis-[triethoxysilylpropyl] tetrasulfide silane pre-treatments on the AZ31 Mg alloy. The silane solution was modified by the addition of cerium nitrate or lanthanum nitrate in order to introduce corrosion inhibition properties in the silane film.The corrosion behaviour of the pre-treated AZ31 magnesium alloy was studied during immersion in 0.005 M NaCl solution, using electrochemical impedance spectroscopy and the scanning vibrating electrode technique (SVET). The electrochemical experiments showed that the presence of cerium ions or lanthanum ions improve the protective behaviour of the silane film. The SVET experiments evidenced that the presence cerium in the silane film led to an important reduction of the corrosion activity.The results demonstrate that either cerium ions or lanthanum ions can be used as additives to the silane solutions to improve the performance of the pre-treatments for the AZ31 magnesium alloy.     

The effect of Cu-rich sub-layer on the increased corrosion resistance of Cu-xZn alloys in chloride containing borate buffer

The electrochemical behaviour of Cu-xZn alloys, as well as their constituent metals, in a borate buffer containing chloride ions in the molar range from 0.01 to 1 M are studied. Characteristics of these materials under anodic polarization are compared and the composition and morphology of the corrosion products formed in the course of polarization experiment are analysed by SEM and EDS. X-ray photoelectron spectroscopy and electrochemical impedance measurements are used for characterization of the surface layers formed on Cu, Zn and Cu-40Zn alloy during 2-h immersion at E_oc in a borate buffer containing two different concentrations of chloride ions. New aspects of the behaviour of brass under E_oc condition are revealed. The improved corrosion resistance of brass in chloride media, if compared to zinc metal, is attributed to a Cu-rich layer formed by the selective dissolution of zinc. Based on the results, a structural model describing the improved corrosion resistance of Cu-40Zn alloy with respect to Zn metal is proposed.     

TiO2 nanostructures synthesized by electrochemical anodization in green protic ionic liquids for photoelectrochemical applications

This work studies the influence of the 2-hydroxyethylammonium acetate (2-HEAA) ionic liquid (IL) as an electrolyte in the electrochemical anodization of titanium for the synthesis of nanostructures for photoelectrochemical water splitting. Different 2-HEAA IL concentrations were used ranging from 0 to 4% v/v (IL-0 to IL-4) in electrolytes containing NH₄F, water and ethylene glycol. Morphological, structural and electrochemical characterization of the nanostructures was carried out by means of field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and Mott-Schottky (MS) analysis. Additionally, photoelectrochemical tests were carried out in order to evaluate the efficiency of these materials as catalysts for water splitting applications. According to the obtained results, the electrolyte used for electrochemical anodization should contain little amount of NH₄F (0.05 M) in order to obtain efficient nanostructures for photoelectrochemical purposes. However, small concentrations of IL (IL-0.25) resulted in nanostructures with higher photocurrents than doubling the NH₄F concentration to 0.1 M. Therefore, the IL addition contributes to a more sustainable electrolyte formulation. The best photoelectrochemical response for water splitting processes was obtained for the nanostructures anodized with 1% v/v of 2-HEAA IL (IL-1) due to their high surface/area (higher pore diameters, smaller nanotubes wall thickness and higher nanotubes lengths), better crystallinity and electrochemical response, showing photocurrents more than 100% higher than the ones obtained for the nanotubes anodized without IL.     

Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D

Protective composite coatings were prepared on magnesium alloy AZ91D by micro-arc oxidation (MAO) treatment plus a top coating with sealing agent using multi-immersion technique under low-pressure conditions. The corrosion resistance of AZ91D alloy with composite coatings was superior evidently to that with merely MAO film. SEM observations revealed that the sealing agent was integrated with MAO film by physically interlocking; therewith covered uniformly the surface as well as penetrated into pores and micro-cracks of MAO film. The anti-corrosion properties in 3.5% NaCl solution of the composite coatings were evaluated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Based on the results of chronopotentiometric (E ∼ t) and EIS measurements for long time immersion in 3.5% NaCl solution, appropriate equivalent circuits for the composite coatings system were proposed. It follows that due to the blocking effect of the sealing agent in pores and cracks in MAO film, the composite coatings can suppress the corrosion process by holding back the transfer or diffusion of electrolyte and corrosion products between the composite coatings and solution during immersion.     

The effects to the structure and electrochemical behavior of zinc phosphate conversion coatings with ethanolamine on magnesium alloy AZ91D

This paper discussed a zinc phosphate conversion coating formed on magnesium alloy AZ91D from the phosphating bath with varying amounts of ethanolamine (MEA). The effects of MEA on the form, structure, phase composition and electrochemical behavior of the phosphate coatings were examined using an scanning electron microscopy (SEM), X-ray diffraction (XRD) potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) measurements. Interpretations of the electrical elements of the equivalent circuit were obtained from the SEM structure of the coatings, assumed to be formed of two layers: an outer porous crystal layer and an inner flat amorphous layer. The result showed that adding MEA refined the microstructure of the crystal layer and that the phosphate coating, derived at the optimal content of 1.2 g/L, with the most uniform and compact outer crystal layer provided the best corrosion protection.     

Influence of substrate composition on corrosion protection of sol–gel thin films on magnesium alloys in 0.6 M NaCl aqueous solution

The corrosion protection behaviour of organic–inorganic hybrid thin films on AZ31 and AZ61 magnesium alloy substrates has been studied. These films were prepared by a sol–gel dip-coating method. The organopolysiloxane precursors were γ-methacryloxypropyltrimethoxysilane (MAPTMS) and tetramethoxysilane (TMOS). An attempt was made to determine the possible relationships between the degradation of the sol–gel film and composition of the metal substrate during the exposure of the metal/coating system to 0.6 M NaCl aqueous solutions. For this purpose electrochemical impedance spectroscopy (EIS) and hydrogen evolution measurements were applied. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the sol–gel films formed on the surface of AZ61 alloy were far more perfect and uniform than those formed on the AZ31 alloy. This behaviour was attributed to the effect of the native oxide film initially present on the surface of the AZ61 alloy, which inhibited the attack of magnesium. Results indicated that the sol–gel coated AZ61 substrate tended to develop corrosion products slower than the sol–gel coated AZ31 substrate, trend that could change by prolonging exposure time. After 6 days of immersion, a clear inhibitive effect of the corrosion products formed during the test was observed in the case of the sol–gel coated AZ31, but not with the coated AZ61 alloy substrate, a phenomenon explained by the carbonate enrichment observed by XPS.     

Al2O3/Si3N4 nanocomposite coating on aluminum alloy by the anodizing route: Fabrication,characterization, mechanical properties and electrochemical behavior

An Al₂O₃/Si₃N₄ nanocomposite coating was successfully fabricated on commercial aluminum alloy. Hardness measurements, polarization and electrochemical impedance spectroscopy (EIS) were employed to study the mechanical and corrosion behaviors of the coatings. Field-Emission Scanning Electron Microscopy (FE-SEM) equipped with Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) were utilized to characterize the surface morphology and phase composition of the coatings. Also, coatings abrasive wear properties were evaluated with a modified ASTM G105 standard. FE-SEM image, EDS and XRD analysis revealed the presence of Si₃N₄ in the coating. Furthermore, the results showed hardness of the coatings to increase from 380±50 HV for the anodized layer to 712±36 HV for the composite coatings that were formed in an electrolyte containing 6 gr/lit Si₃N₄ nanoparticles. Electrochemical measurements indicated that corrosion resistance of the nanocomposite coating significantly increased compared to the anodized coating. In addition, the effect of Si₃N₄ nanoparticles into the nanocomposite coatings on abrasive wear mechanism and mass loss rate of the coatings was investigated.     

Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media

The influence of the microstructure and aluminium content of commercial AZ31, AZ80 and AZ91D magnesium alloys was evaluated in terms of their corrosion behaviour in an aerated 3.5 wt.% NaCl solution at 25 °C. The corrosion process was monitored by electrochemical impedance spectroscopy (EIS). The surface was characterized by scanning electron microscopy (SEM), scanning Kelvin probe force microscopy (SKPFM) and low-angle X-ray diffraction (XRD). The extent of corrosion damage was strongly dependent on the aluminium content and alloy microstructure. Two key factors were observed for the lowest corrosion rates, which occurred for the AZ80 and AZ91D two-phase alloys: the aluminium enrichment on the corroded surface for the AZ80 alloy, and the β-phase (Mg₁₇Al₁₂), which acted as a barrier for the corrosion progress for the AZ80 and AZ91D alloys. Surface potential maps suggested that, between the β-phase and the α-matrix, the galvanic coupling was not significant.     

Composite anticorrosion coatings for AZ91D magnesium alloy with molybdate conversion coating and silicon sol–gel coatings

This study evaluated the corrosion resistance of AZ91D magnesium alloy coated by composite coatings which consisted of a molybdate conversion coating and three layers of silicon sol–gel coatings. For molybdate conversion treatment, various conditions including the pH of the molybdate baths, immersion time and bath temperature were investigated using electrochemical measurements. The corrosion resistance of the AZ91D magnesium alloy was improved to some extent by the conversion coating with the optimal conversion parameters (7.3 g/L (NH₄)₆Mo₇O₂₄·6H₂O solution with pH 5 for 30 min at 30 °C).     

Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings

In this paper, the results on the electrochemical impedance spectroscopy and corrosion properties of electrodeposited nanostructured Al₂O₃-Ni composite coatings are presented. The nanocomposite coatings were obtained by codeposition of alumina nanoparticles (13 nm) with nickel during plating process. The coating thickness was 50 μm on steel support and an average of nano Al₂O₃ particles inside of coatings at 15 vol.% was present. The structure of the coatings was investigated by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure. The electrochemical behavior of the coatings in the corrosive solutions was investigated by polarization potentiodynamic and electrochemical impedance spectroscopy methods. As electrochemical test solutions 0.5 M sodium chloride and 0.5 M potassium sulphate were used in a three electrode open cell. The corrosion potential is shifted to more negative values for nanostructured coatings in 0.5 M sodium chloride. The polarization resistance in 0.5 M sodium chloride decreases in 24 h, but after that increases slowly. In 0.5 M potassium sulphate solution the polarization resistance decreases after 2 h and after 30 h of immersion the polarization resistance is higher than that of the beginning value. The corrosion rate calculated by polarization potentiodynamic curves obtained after 30 min from immersion in solution is smaller for nanostructured coatings in 0.5 M potassium sulphate (4.74 μm/year) and a little bit bigger in 0.5 M sodium chloride (5.03 μm/year).     

Effect of the experimental setup in the behaviour of sol–gel coatings

Electrochemical behaviour of the sol–gel-coated AA2024-T3 samples was evaluated using electrochemical impedance spectroscopy (EIS) in a three-electrode arrangement cell using Na₂SO₄ 0.1 M solution as electrolyte. The effect of the reference electrode leakage was examined using as reference a low-leakage Ag/AgCl electrode and a platinum wire. The results show that very low-chloride concentrations in solution are able to induce heavy dissolution of intermetallic precipitates. That corrosion process masks information on the barrier properties of sol–gel coatings otherwise available through EIS measurements.