Influence of pH on the deterioration of plasma electrolytic oxidation coated AM50 magnesium alloy in NaCl solutions

The corrosion deterioration process of plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy prepared from two different based electrolytes, i.e., an alkaline phosphate electrolyte and an acidic fluozirconate electrolyte, were investigated using electrochemical impedance spectroscopy (EIS) in a 0.1 M NaCl solution with pH of 3, 7 and 11, respectively. It was found that the PEO coating formed in alkaline phosphate electrolyte, which was composed mainly of MgO, suffered from rapid chemical dissolution and lost its protection capability very quickly in acidic NaCl solution (pH 3). The chemical dissolution of this PEO coating was retarded in neutral NaCl solution (pH 7) and the corrosion damage was localized in this environment. On the other hand, in the alkaline NaCl solution (pH 11), the MgO coating underwent only slight degradation. The PEO coating produced in acidic fluozirconate electrolyte, the failure was marked by the flaking-off of the large areas of coating in acidic NaCl solution (pH 3). However, in the neutral and alkaline NaCl solutions, the coating underwent only a slight degradation without any observable corrosion damage in the 50 h test. The results showed that the deterioration process of PEO coated magnesium alloy was governed mostly by the pH of NaCl solution and it was also strongly related to the microstructure and composition of the PEO coatings.     

Corrosion behavior of the composite ceramic coating containing zirconium oxides on AM30 magnesium alloy by plasma electrolytic oxidation

The deterioration process of a plasma electrolytic oxidation (PEO) coating containing zirconium oxides on AM30 magnesium alloy in 3.5 wt.% NaCl solution have been investigated. The coating consists of an outer porous layer and an inner dense layer. The content of MgF₂ is high in the pores and an MgO-rich layer is evident in the inner layer. The corrosion resistance of the outer layer gradually decreases in the initial immersion stage (96 h) due to the decomposition of MgO, and the deterioration of the inner layer is delayed by the blocking effect of the outer layer.     

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.     

Electrolytic MgO/ZrO2 duplex-layer coating on AZ91D magnesium alloy for corrosion resistance

By a two-step fabrication process of electrolytic deposition and annealing treatment, an MgO/ZrO₂ duplex-layer coating has been prepared on AZ91D magnesium alloy as a protective film against corrosion. Owing to the chemical bonding formed after the condensation of precursory hydroxides, the adhesion strength, thickness and compactness of MgO coating on the substrate are significantly enhanced by the intermediate ZrO₂ layer which prevents the formation of corrosion product Mg₂(OH)₃Cl·4H₂O. As a result, the MgO/ZrO₂ duplex-layer coated specimen reveals relatively high corrosion resistance and superior stability in 3.5 wt% NaCl solution with respect to the MgO single-layer coated specimen.     

Microstructure, spallation and corrosion of plasma sprayed Al2O3–13%TiO2 coatings

The electrochemical corrosion behaviours of the steel substrates coated with three different plasma sprayed Al₂O₃–13%TiO₂ coatings were studied in this paper. The three kinds of Al₂O₃–13%TiO₂ coatings were conventional ME coating, nanostructured NP coating and NS coating. There were micro cracks, laminar splats and straight columnar grains in ME coating. For the two nanostructured coatings, the laminar microstructure and columnar grains were not obvious. The NP coating had the highest hardness and spallation resistance. Electrochemical corrosion behaviour of the three coatings was mainly investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in aqueous Na₂SO₄ solution.     

Effect of plasma electrolytic oxidation coating on the stress corrosion cracking behaviour of wrought AZ61 magnesium alloy

An attempt was made to understand the effect of silicate based plasma electrolytic oxidation (PEO) coating on the stress corrosion cracking (SCC) behaviour of an AZ61 wrought magnesium alloy. The SCC behaviour of untreated and PEO coated specimens was assessed using slow strain rate tensile tests at two different nominal strain rates, viz. 1 × 10⁻⁶ s⁻¹ and 1 × 10⁻⁷ s⁻¹, in ASTM D1384 test solution at ambient conditions. The PEO coating was found to improve the general corrosion resistance to a significant extent; however, the improvement in the resistance to stress corrosion cracking was only marginal.     

Enhanced corrosion protection of MgO coatings on magnesium alloy deposited by an anodic electrodeposition process

MgO coatings were prepared on magnesium alloy surface by an anodic electrodeposition process in concentrated KOH solution followed by heat treatment in air. The phase composition and microstructure of the as-formed MgO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behavior of the MgO-coated samples was evaluated by electrochemical measurements and immersion tests in Hanks’ solution. The results showed that the MgO-coated Mg alloy exhibited a much superior stability and lower corrosion rate, and thus enabled to improve the corrosion resistance, whereas the bare Mg alloy suffered from severely localized corrosion attack.     

Effect of tin modification on corrosion of AM70 magnesium alloy

In this study, AM70 magnesium alloys with and without 2 wt.% Sn addition are compared for their corrosion performance. They are found to have similar corrosion rates in the first 70 h in 5 wt.% NaCl solution, but in extended immersion test the Sn modified AM70 exhibits accelerated overall corrosion. Nevertheless, Sn modification significantly decreases the susceptibility of the alloy to localized corrosion attack. Polarization curve measurements further indicate that the Sn modified AM70 is likely to have worse galvanic corrosion than AM70 in terms of the loss of metal, but again the Sn modification makes the galvanic corrosion less localized, which is an improvement aspect of the galvanic corrosion performance. The effect of Sn addition on the corrosion behavior appears to be associated with the presence of Sn-containing particles and the solute Sn in the matrix phase, which may change the electrochemical anodic and cathodic polarization behavior of the alloy.     

Characterization and corrosion studies of ceria thin film based on fluorinated AZ91D magnesium alloy

The CeO₂ thin film was prepared via sol-gel method on fluorinated AZ91D magnesium alloy surfaces. The surface morphology, composition and the corrosion resistance of the film were investigated in details using scanning electron microscope, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy as well as potentiodynamic polarization tests. It was found that small amount of MgO and MgF₂ were encapsulated in CeO₂ thin film. The electrochemical measurement results demonstrated that the CeO₂ thin film on fluorinated AZ91D magnesium alloy could improve the corrosion resistance approximately by two orders of magnitude compared with that of the bare substrate.     

Formation of dicalcium phosphate dihydrate on magnesium alloy by micro-arc oxidation coupled with hydrothermal treatment

A layer containing dicalcium phosphate dihydrate (DCPD) and β-Ca₃(PO₄)₂ was prepared on magnesium alloy by hydrothermal treatment of micro-arc oxide (MAO) layer. The biocorrosion resistance of the oxide layers before and after hydrothermal treatment was analyzed by anodic polarization and electrochemical impedance spectroscopy (EIS) in Hank’s solution. The prepared MAO layers consisted mainly of MgO and MgAl₂O₄, and Ca and P inside the oxide layers existed with amorphous phase. Hydrothermal treatments not only made the amorphous Ca and P change into DCPD and β-Ca₃(PO₄)₂ crystals, but also improved the biocorrosion resistance of magnesium alloys, especially the pitting corrosion resistance.     

In-situ study of the formation process of stannate conversion coatings on AZ91D magnesium alloy using electrochemical noise

The formation process of stannate conversion coating (CC) on AZ91D alloy was in-situ investigated by electrochemical noise (EN). The wavelet transform, as well as noise resistance (R_n) and spectral noise resistance (R_sn), had been employed to analyze the EN data. It was revealed that there exist two distinguishing stages of stannate CC formation process on AZ91D alloy, including an incubation stage companying with the nucleation and nuclei dissolution process, a periodical growth stage involving hemispherical particles growth and coating dissolution process. Furthermore, the results demonstrated that EN was a powerful tool to investigate rapid electrochemical process, such as CC formation process.     

Characterisation of fresh surface oxidation films formed on pure molten magnesium in different atmospheres

This paper examines the early stages of surface oxidation of liquid magnesium under argon, air, and air mixed with protective fluorine-bearing gases. Surface film characteristics such as morphology, thickness and composition are determined. In all cases except argon the film was locally uniform with no evidence of specific nuclei.In air, the film thickness was 15-150 nm. Under fluorine-bearing gas mixtures the surface film was a mixed fluoride and oxide and more even: 70-100 nm thick under SF₆ and 30-50 nm under 1,1,1,2-tetrafluoroethane. The latter had a substantially lower O:F ratio. Complete conversion of available fluorine into the film was indicated.     

Formation of micro-arc oxidation coatings on AZ91HP magnesium alloys

In a neutral solution, coating formation by micro-arc oxidation (MAO) on AZ91HP magnesium alloy was studied. The process involved the substrate dissolution and coating development. During the first 5 s, the sample mass decreased, indicating substrate dissolution dominating the process. After 5 s, the sample mass began to increase and the coating development began to predominate the process. The coating was firstly nucleated on α phase and sparks initially appeared mainly on the edges of the sample. With treating proceeded, the coating was becoming uniform; meanwhile, microscopic pores of anodic coatings increased in size and decreased in number.     

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.     

Corrosion evaluation of microarc oxidation coatings formed on 2024 aluminium alloy

Dense alumina ceramic coatings of 7 μm thickness were fabricated on 2024 aluminium alloy by microarc oxidation (MAO). The corrosion behaviour of the MAO coated alloys was evaluated using potentiodynamic polarisation and EIS measurements. The results show that the corrosion process of the coated alloy can be divided into three stages: (1) the initial stage (the first 2-6 h of immersion): penetration of corrosion medium into the aluminium alloy was inhibited by coating; (2) the second stage (after 24 h of immersion), corrosion medium penetrated to attack the interface between the substrate and the coating; (3) the final stage (after about 96 h): corrosion process was controlled by the diffusion of corrosion products.     

On the degradation mechanism of corrosion protective poly(ether imide) coatings on magnesium AZ31 alloy

In previous publications of the authors, good performance of poly(ether imide) as corrosion protective coatings for magnesium AZ31 alloy was reported. It was suggested that during the sample degradation magnesium hydroxide could react with the imide ring forming magnesium polyamate and polyamic acid, but this could not be experimentally confirmed. In the present letter, we confirm the occurrence of this reaction by infrared and X-ray photoelectron spectroscopy and discuss its influence in the corrosion behavior observed in electrochemical impedance spectroscopy tests.     

The influence of the microstructure on the atmospheric corrosion behaviour of magnesium alloys AZ91D and AM50

Even though magnesium, as a structure metal, is most commonly used in an atmospheric environment, most investigations of magnesium are performed in solution. In the present work the atmospheric corrosion of two commonly used magnesium alloys, AZ91D and AM50, has been investigated from the initial stages up to the most severe forms of corrosion. A detailed investigation of the morphology of a corrosion attack and its development over time shows that the atmospheric corrosion mechanism is similar for the two alloys. Based on these findings a schematic model of the initial atmospheric corrosion attack on AZ91D is presented and discussed.     

Corrosion behaviour of a magnesium matrix composite with a silicate plasma electrolytic oxidation coating

The corrosion behaviour of AZ92 magnesium alloy reinforced with various volume fractions of silicon carbide particles (SiCp) and treated by alternating current (AC) plasma electrolytic oxidation (PEO) was investigated in humid and saline environments. For untreated composites, corrosion attack started around the Al-Mn inclusions and gradually developed into general corrosion without significant galvanic coupling between the matrix and the SiCp. PEO coatings consisted mainly of MgO and Mg₂SiO₄, and revealed increased hardness, reduced thickness and slightly higher corrosion resistance with increasing proportion of reinforcement. Pit formation and hydration of the outer layer were the main mechanisms of corrosion of PEO-treated specimens.     

Electrochemical investigation of the influence of laser surface melting on the microstructure and corrosion behaviour of ZE41 magnesium alloy – An EIS based study

Surface melting of a magnesium alloy, ZE41 (4%-Zn, 1%-RE) was performed to achieve electrochemical homogeneity at the surface by microstructure refinement. Large secondary precipitates are particularly known to cause severe pitting in magnesium alloys. The corrosion resistance of the laser treated and untreated alloy was investigated by potentiodynamic polarisation and electrochemical impedance spectroscopy. Contrary to the reported behaviour of other magnesium alloys (such as AZ series alloys), laser surface melting did not significantly improve the corrosion resistance of ZE41. This observation is attributed to the absence of beneficial alloying elements such as Al in ZE41 alloy.     

Effect of antimony, bismuth and calcium addition on corrosion and electrochemical behaviour of AZ91 magnesium alloy

This study investigated the effect of antimony, bismuth and calcium addition on the corrosion and electrochemical behaviour of AZ91 magnesium alloy in 3.5% NaCl solution. Techniques including constant immersion, electrochemical potentiodynamic polarisation, scanning electron microscopy (SEM), energy dispersed spectroscopy (EDS) and X-ray diffraction (XRD) were used to characterise electrochemical and corrosion properties and surface topography. It was found that corrosion attack occurred preferentially on Mg₃Bi₂ and Mg₃Sb₂ particles while Mg₁₇Al₈Ca_0.5 and Mg₂Ca phases showed no detrimental effect on corrosion. Combined addition of small amounts of bismuth and antimony to the AZ91 alloy resulted in significant increase in corrosion rate.