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 behaviour of magnesium in ethylene glycol

Corrosion of magnesium engine components by coolant is an important issue in the automotive industry where magnesium alloys may be used. It is of significance to understand the corrosion behaviour of pure magnesium in ethylene glycol solutions, as this can provide a basis for developing new coolants for magnesium alloy engine blocks. In this paper, through corrosion and electrochemical tests, it was found that the corrosion rate of magnesium decreased with increasing concentration of ethylene glycol. Individual contaminants, such as NaCl, NaHCO₃, Na₂SO₄ and NaCl can make aqueous ethylene glycol solution more corrosive to magnesium. However, in NaCl contaminated ethylene glycol, NaHCO₃ and Na₂SO₄ showed some inhibition effect. The solution resistivity played an important role in the corrosion of magnesium in ethylene glycol solutions, and the competitive adsorption of ethylene glycol and the contaminants on the magnesium surface was also responsible for the observed corrosion behaviours. The corrosion of magnesium in ethylene glycol can be effectively inhibited by addition of fluorides that react with magnesium and form a protective film on the surface.     

Influence of cerium molybdate containers on the corrosion performance of epoxy coated aluminium alloys 2024-T3

Cerium molybdate containers loaded with 2-mercaptobenzothiazole were incorporated into epoxy coatings onto aluminium alloys 2024-T3 and investigated with respect to the corrosion protection of the metallic surfaces. The coatings were deposited via the dip-coating process. The morphology of the coatings was examined by Scanning Electron Microscopy. Their composition and structure were investigated by Fourier Transform Infrared Spectroscopy and Energy Dispersive X-ray Analysis. The corrosion resistance of these coatings was investigated by using electrochemical impedance spectroscopy and open circuit potential. After exposure to 0.05 M NaCl solution for 28 days, the coatings with the loaded containers exhibit improved corrosion performance.     

Corrosion protection of magnesium AZ31 alloy using poly(ether imide) [PEI] coatings prepared by the dip coating method: Influence of solvent and substrate pre-treatment

In this study, investigations on the protectiveness of poly(ether imide) coatings against corrosion of magnesium AZ31 alloy sheets are performed. The coatings were prepared in different pre-treated substrates by the dip coating method using N′N′-dimethyl acetamide (DMAc) and N′-methyl pyrrolidone solutions. The optimal performance was obtained for hydrofluoric acid treated substrates coated using DMAc solution (coating thickness 13 μm) which showed impedances in the order of 10⁷ Ω cm² even after more than 3300 h of exposure to a 3.5 wt.% NaCl solution. This high performance is associated to an acid–base interaction at the interface as observed by X-ray photoelectron spectroscopy.     

Electrochemical corrosion behaviour of Mg–Al alloys with thermal spray Al/SiCp composite coatings

The corrosion protection of Mg–Al alloys by flame thermal spraying of Al/SiC particles (SiCp) composite coatings was evaluated by electrochemical impedance spectroscopy in 3.5 wt.% NaCl solution. The volume fraction of SiCp varied between 5 and 30%. The as-sprayed Al/SiCp composite coatings revealed a high number of microchannels, largely in the vicinity of the SiCp, that facilitated the penetration of the electrolyte and the subsequent galvanic corrosion of the magnesium substrates. The application of a cold-pressing post-treatment reduced the degree of porosity of the coatings and improved the bonding at the coating/substrate and Al/SiC interfaces. This resulted in improved corrosion resistance of the coated specimens. The effectiveness of the coatings slightly decreased with the addition of 5–30 vol.% SiCp compared with the unreinforced thermal spray aluminium coatings.     

用丝束电极研究SO_4~(2-)对纯铝缝隙腐蚀的影响

采用动电位极化和丝束电极技术测量了纯铝在2mol/L NaCl和2mol/L NaCl 0.8mol/L Na2SO4溶液中的极化曲线、缝隙内外的自腐蚀电位和电化学阻抗分布,研究了SO42-对铝缝隙腐蚀的影响。结果表明,在NaCl溶液中,缝隙内的铝为阳极、缝隙外为阴极;随浸泡时间增加,腐蚀不均匀性增加。加入Na2SO4后,减小了缝隙内外腐蚀电位差,显著降低了铝的腐蚀速度。Na2SO4是中性溶液中铝的吸附型缓蚀剂,延缓了缝隙腐蚀的发生。     

Effect of microcrystallization on pitting corrosion of pure aluminium

A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the corrosion potential of the sample shifted towards more positive direction, while its corrosion current density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium.     

Wire-array-applied ultrafine tungsten wire coated with Al–Mg alloy layer via electron beam evaporation

Al–Mg alloy coatings were deposited onto superfine tungsten wire substrates via electron beam deposition at electronic beam currents ranging from 80 to 120?mA. The effects of electronic beam currents and baking process on the surface characteristics of the aluminium–magnesium alloy coatings were investigated using scanning electron microscopy. Energy-dispersive X-ray was also used to investigate the composition of the coatings according to the chemical components of the source materials. X-ray diffraction results suggested that the Al–Mg alloy coatings consisted of an Al₁₂Mg₁₇ intermetallic compound and pure aluminium phase. Electrochemical measurements determined the corrosion protection performance of the aluminium–magnesium alloy coatings with different magnesium contents. Specimen tensile properties were related to electron beams and surface roughness. The anti-corrosion performance of the coatings was increased with magnesium content.     

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.     

Overall micro-arc oxidation treatment for AZ31B–6061 magnesium–aluminium dissimilar metal connecting parts

The magnesium–aluminium connecting parts are important application form for lightweight structural materials. But the conductive connect of magnesium and aluminium will cause serious galvanic corrosion problems. Therefore, the overall corrosion protective treatment is necessary. A ceramic coating was prepared via overall micro-arc oxidation to wrap the magnesium–aluminium connecting part integrally. The surface morphologies and compositions of the coatings were analysed by scanning electron microscopy and X-ray energy dispersive spectroscopy. The corrosion behaviour of the coatings was investigated with potentiodynamic polarisation tests in 3.5?wt-% NaCl solution. The growth process of ceramic coating on aluminium and magnesium surface was investigated, which showed the micro-arc oxidation reaction priority and the balanced growth process of ceramic coating under unbalanced micro-arc distribution. The results demonstrated that the overall micro-arc oxidation treatment improved the corrosion resistance and reduced the corrosion potential difference of each metal of magnesium–aluminium connecting part.     

Corrosion electrochemical behaviors of silane coating coated magnesium alloy in NaCl solution containing cerium nitrate

Sol–gel coatings cannot provide adequate corrosion protection for metal/alloys in the corrosive environments due to their high crack‐forming potential. This paper demonstrates the possibility to employ cerium nitrate as inhibitor to decrease the corrosion development of sol–gel‐based silane coating on the magnesium alloy in NaCl solution. Cerium nitrate was added into the NaCl solution where the silane coating coated magnesium alloy was immersed. Scanning electron microcopy (SEM) was used to examine surface morphology of the silane coating coated magnesium alloy immersed in NaCl solutions doped and undoped with cerium nitrate. The corrosion electrochemical behaviors were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. The results showed that the introduction of cerium nitrate into NaCl solution could effectively inhibit the corrosion of the silane coating coated magnesium alloy. Moreover, the influence of concentration of cerium nitrate on the corrosion inhibition and the possible inhibiting mechanism were also discussed in detail.     

Corrosion behaviour of Mg/Al alloys with composite coatings

The corrosion behaviour of aluminium/silicon carbide (Al/SiC) composite coatings deposited by thermal spray on AZ31, AZ80 and AZ91D magnesium-aluminium alloys was investigated by electrochemical and gravimetric measurements in 3.5 wt.% NaCl solution at 22 °C. Corrosion products were examined by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and low-angle X-ray diffraction (XRD). Al/SiC composite coatings in the as-sprayed state revealed high level of porosity with poor bonding at the Al/SiC and coating/substrate interfaces, which facilitated degradation of the magnesium substrates by a mechanism of galvanic corrosion. Cold-pressing post-treatment produced more compact coatings with improved corrosion performance in 3.5 wt.% NaCl compared with as-sprayed coatings.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

Corrosion protection of aluminium pretreated by vinyltriethoxysilane in sodium chloride solution

The corrosion protection of vinyltriethoxysilane (VTES) films on aluminium during exposure to 3% NaCl was investigated using electrochemical impedance spectroscopy (EIS), potential-time measurements and optical microscopy coupled with image analysis. Composition and thickness of films were analyzed using Auger electron spectroscopy (AES) combined with depth profiling. It was shown that films deposited from 5% solution were significantly thicker and exhibited lower porosity and better corrosion stability, as compared to films deposited from 2 vol.% solution. VTES films deposited from 5 vol.% solutions and cured for 30 min exhibited better protection properties than other investigated films.     

Corrosion and wear properties of multipurpose coatings deposited by ion-beam-assisted deposition

Electrochemical measurements and wear tests were performed on aluminium and aluminium alloy coatings containing magnesium for uniform and local pitting corrosion protection of low carbon steel substrates. Final hard chromium nitride and aluminium nitride layers were deposited at the surface of the protective films in order to lower friction and wear. The results show that wear and corrosion protection can be improved by use of bifunctional multilayers. The coatings for multipurpose application were generated by ion-beam-assisted deposition. The defined intrinsic film stress controlled by the ion-to-atom arrival ratio influences the corrosion properties. Increasing the ion-to-atom ratios usually improves the corrosion resistance.     

A study on mechanism of corrosion protection of polyaniline coating and its failure

Polyaniline (PANI) coatings were electrochemically deposited on substrates of stainless steel and platinum in solutions of 0.2 M H₂SO₄ and 0.1 M aniline by cyclic voltammetry. The corrosion protection of the PANI coatings and their failure were investigated in 0.2 M H₂SO₄ solution. It was observed that the corrosion protection ability of the coating to steel substrate was increased with the increase of the coating thickness. The corrosion protection ability was mainly attributed to the passivating effect of PANI due to its oxidizing ability in its emeraldine state. During its operation, the PANI coating in emeraldine state tended to gradually lose its corrosion protection ability. This gradual failure of the PANI coating, but faster than expected, was confirmed to be related to a gradual reduction of the emeraldine PANI and a gradually increased resistance between the PANI coating and the stainless steel substrate. These findings lead to a new mechanism for the corrosion protection of PANI coating and its failure.     

Corrosion behaviour of thermally sprayed Al and Al/SiCp composite coatings on ZE41 magnesium alloy in chloride medium

Thermally sprayed Al and Al/SiCp composite coatings have been deposited on ZE41 magnesium alloy and mechanical compaction at room temperature was applied to the Al and Al/SiCp coatings to reduce their porosity. Corrosion behaviour of coated samples was evaluated and compared to that of uncoated substrate in 3.5 wt.% NaCl solution using electrochemical measurements. Al and Al/SiCp composite coatings reduced the corrosion current density of Mg-Zn alloys by three and two orders of magnitude, respectively, and reductions up to four orders of magnitude were obtained after mechanical compaction.     

三种不同电解液中镁微弧氧化膜研究

在氟锆酸盐、铝酸盐和硅酸盐3种不同电解液中对镁进行微弧氧化处理分别制得了锆膜、铝膜和硅膜, 对这些膜层的形貌、相组成、表面粗糙度、结合强度、硬度和耐蚀性进行了研究。结果表明：锆膜致密,由t-ZrO2、MgF2和Mg2Zr5O12相组成;铝膜多孔,由MgAl2O4和MgO相组成;硅膜多孔,由Mg2SiO4和MgO相组成。这些膜层表面很粗糙,膜层与基体结合非常牢固。铝膜的硬度比锆膜和硅膜更高。经微弧氧化处理后镁的耐蚀性得到了明显改善,其中锆膜的耐蚀性最好。     

SiO2 based hybrid inorganic–organic films doped with TiO2–CeO2 nanoparticles for corrosion protection of AA2024 and Mg-AZ31B alloys

Hybrid sol–gel coatings provide an approach as protective layers on metals. In this work, corrosion protection of aluminium and magnesium alloys by SiO₂-methacrylate coatings doped with TiO₂–CeO₂ nanoparticles was studied. The films show an improvement of the barrier properties at initial immersion. The reactivity of both alloys produces a deterioration of the protection with longer immersion, although TiO₂–CeO₂ nanoparticles let to observe signals of self-healing effect. Aluminium oxide/sol–gel interface was found to be stable. In combination with excellent paint adhesion on sol–gel films, these coatings can be a promising alternative pre-treatment for high strength aluminium alloys prior to painting.     

Scratch-resistant anticorrosion sol-gel coating for the protection of AZ31 magnesium alloy via a low temperature sol-gel route

A novel hybrid sol-gel/polyaniline coating has been developed for application onto an AZ31 magnesium alloy for corrosion protection. Electrochemical Impedance Spectroscopy in 3.5 wt% NaCl and diluted Harrison’s solutions, along with salt spray tests showed that the coating possesses excellent corrosion resistance. The hybrid coating was modified by doping with silica nanoparticles (for scratch resistance) and cured at a low temperature of 75 °C. Whilst conventional sol-gel methods tend to limit the coating thickness values up to 10 μm, the new hybrid sol-gel/polyaniline system presented here allows thick coatings to be deposited, in this case, around 50-60 μm.