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.     

电流密度对镁合金微弧氧化膜层性能的影响

在电流密度分别为3、6、9、12 A/dm2时,用微弧氧化的方法在碱性电解液体系中制备了镁合金微弧氧化膜,考察了不同电流密度对生成的氧化膜层厚度、硬度的影响规律;用XRD分析了氧化膜层的相结构;并采用NaCl溶液浸泡试验和中性盐雾试验,考察了氧化膜的耐蚀性能。结果显示:随着电流密度的增大,膜层的厚度、硬度均呈增加的趋势;陶瓷层主要由MgO、Mg2SiO4和非晶相组成;得到的氧化膜层具有优良的耐蚀性能。     

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.     

Plasma anodized ZE41 magnesium alloy sealed with hybrid epoxy-silane coating

Anodic coatings on magnesium ZE41 alloy were formed by DC plasma electrolytic oxidation (PEO) in spark regime in solution composed of NaOH, Na₂SiO₃ and KF. The positive effect of poly(ethylene oxide) addition into the anodizing electrolyte on PEO process, anodic film porosity and its protective performance was described. Anodic films were sealed with hybrid epoxy-silane formulation. The corrosion behavior of the coated ZE41 was studied through electrochemical impedance spectroscopy (EIS) in 0.6 M NaCl solution. Resulting duplex PEO/epoxy-silane coating provides good protective performance without significant signs of corrosion during 1 month of immersion test.     

Investigation of Corrosion Protection Performance of Multiphase PEO (Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, MgO,MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>) Coatings on Mg Alloy Formed in Aluminate-Silicate- based Mixture Electrolyte

Plasma electrolytic oxidation (PEO) coatings in the aluminate-silicate-based mixture electrolyte solution with different duty cycles were successfully applied on Mg alloy. The corrosion behavior of the samples was evaluated by water contact angle test, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and immersion tests. Hydrophobic PEO coating could be obtained by adjusting the duty cycle of the applied electric signal. This coating considerably diminished the Mg dissolution and could enhance the impedance values of Mg alloy in 3.5 wt % NaCl solution. However, the surface of other PEO coated samples showed more hydrophilic properties compared to that of the uncoated sample. Dense structure of the modified PEO multiphase (including Mg₂SiO₄, MgO and MgAl₂O₄ phases) coating and also its appropriate thickness provided an effective barrier to remarkably delay corrosive solution penetration into the PEO coating. This phenomenon led to major decrease in anodic current density of alloy in chloride solution.     

Investigation of wear and corrosion resistance of nanocomposite coating formed on AZ31B Mg alloy by plasma electrolytic oxidation

Ceramic-WC coatings were prepared on AZ31 B Mg alloy by plasma electrolytic oxidation (PEO) from a phosphate based bath containing suspended tungsten carbide nanoparticles at various process times. Scanning electron microscope results indicated that increase of coating time and incorporation of tungsten carbide into the ceramic coating during the PEO process led to a decrease in the number and diameter of coating pores. Phase analysis showed that the nanocomposite coating was composed of MgO, Mg₃(PO₄)₂ and WC. Tribological properties and corrosion behaviour of uncoated AZ31 B Mg alloy and ceramic coatings were evaluated using a pin-on-disc tribometer and potentiodynamic polarisation technique in 3.5% NaCl solution, respectively. The wear and electrochemical tests showed that wear and corrosion resistance of ceramic-WC nanocomposite coatings were better than ceramic only ones. In addition, wear and corrosion behaviour of coatings improved with increasing the coating time.     

压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为

采用电化学方法研究了压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为,并用扫描电镜观察了腐蚀形貌,对腐蚀产物进行了能谱分析.研究结果表明:在酸性溶液环境下,随着Cl-浓度的升高,镁合金的平衡腐蚀电位降低,线性阻抗减小,腐蚀电流增大;随着pH值的减小,晶界出现腐蚀开裂现象;富Al相的耐蚀性高于基体相,在酸性环境中,腐蚀产物主要为MgO和Mg(OH)2     

Preparation and characterization of inorganic and organic coatings on AZ91D magnesium alloy with electroless plating pretreatment

In this paper, a protective coating scheme was applied for the corrosion protection of AZ91D magnesium alloy. Electroless Ni coating (EN coating) as bottom layer, electrodeposited Ni coating (ENN coating), and silane‐based coating (ENS coating) as top layer, respectively, were successfully prepared on AZ91D magnesium alloy by combination techniques. Scanning electron microscopy and X‐ray diffraction were employed to investigate the surface and phase structure of coatings, respectively. The electrochemical corrosion behaviors of coatings in neutral 3.5 wt% NaCl solution were evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The corrosion testing showed that the three kinds of coatings all could provide corrosion protection for AZ91D magnesium alloy to a certain extent, and the corrosion resistance of ENN and ENS was superior to EN. In order to further study the corrosion protection properties of ENN and ENS, a comparative investigation on the evolution of EIS of ENN and ENS was carried out by dint of immersion test in neutral 3.5 wt% NaCl solution. The results indicated that, compared with ENN, the ENS could provide longer corrosion protection for AZ91D magnesium alloy. It is significant to determine the barrier effect of each coating, which could provide reference for industry applications.     

AM50镁合金表面含氧化锆的微弧氧化复合涂层的形成过程(英文)

采用扫描电镜(SEM)和电子衍射能谱(EDX)研究在含K2ZrF6的溶液中AM50镁合金表面复合微弧体氧化涂层的形成过程。采用电化学阻抗谱(EIS)研究在微弧体氧化制备膜层过程中膜层耐腐蚀性能的变化。结果表明:当电压小于起弧电压时,合金表面膜层的主要成分为MgO和MgF2;当施加电压超过起弧电压时,锆氧化物开始在合金表面沉积,且膜层的耐腐蚀性随着电压的升高而提高。     

Corrosion behaviour of molybdate–phosphate–silicate coatings on galvanized steel

In this work, a Cr-free conversion layer based on molybdate–phosphate–silicate (MPS) was synthesised on a galvanized steel by simple immersion and its corrosion behaviour was compared to that of a typical chromate layer. Stationary electrochemical techniques and electrochemical impedance spectroscopy (EIS) were employed to highlight the corrosion mechanisms of both coatings in different NaCl concentrations, immersion times and pH. Contrary to the chromate layer, the MPS coating showed good electrochemical stability even in concentrated NaCl solutions and remarkable electrochemical efficiency. With increasing time, two corrosion stages were associated with the two likely sublayers of the MPS coating. Furthermore, the MPS coating behaved better than the chromate layer in acidic and alkaline pH, especially the latter as a compact corrosion product layer formed. Finally, each coating/electrolyte interface was characterised by an electrical equivalent circuit giving a satisfactory correlation between the experimental and the calculated impedance. It derived that the MPS could be an environmentally friendly alternative to chromating.     

NH4F浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响

目的 考察乙二醇-氟化铵电解液中氟化铵浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响,提高镁合金氟化物膜层的耐腐蚀性能。方法 在含不同浓度NH4F的EG-NH4F电解液中,采用微弧氧化的方法制备氟化物膜层,NH4F质量浓度分别为40、60、80、100、120 g/L。通过扫描电子显微镜(SEM)、X射线能量色散谱仪(EDS)和X射线衍射仪(XRD),对膜层表面微观形貌和成分组成进行分析,并通过电化学测试表征了膜层的腐蚀防护性能,通过盐雾试验评估了膜层长效防腐蚀行为,通过SEM和EDS表征了腐蚀形貌和腐蚀产物。结果 在EG-NH4F中制备膜层的物相组成主要是MgF2。随着NH4F浓度的提高,微弧氧化的起弧电压与工作电压均逐渐减小,膜层中氟含量逐渐增加,膜层的孔径减小,孔数量分布更加均匀,膜层表面粗糙度降低。质量浓度为100 g/L NH4F的膜层自腐蚀电流密度(Jcorr)为2.226×10^‒7 A/cm²,较镁合金基材降低了1个数量级,极化电阻Rp增大到90.156 kΩ.cm²,其阻抗模量|Z|f=0.01 Hz=8.55×10⁵ Ω.cm²,与镁合金基材的阻抗模量|Z|f=0.01 Hz=8.86×10² Ω.cm²相比,提高了3个数量级。结论 微弧氧化处理能够显著改善AZ31镁合金的腐蚀防护性能。NH4F浓度的增加有利于提高膜层的耐腐蚀性能,质量浓度为100 g/L NH4F的膜层耐腐蚀性能最优。     

Environmentally assisted cracking behaviour of plasma electrolytic oxidation coated AZ31 magnesium alloy

Abstract

A wrought AZ31 magnesium alloy was plasma electrolytic oxidation (PEO) coated in phosphate and silicate based alkaline electrolytes. The effect of these PEO coatings on the stress corrosion cracking (SCC) behaviour of the alloy was investigated by slow strain rate tensile (SSRT) tests in ASTM D1384 solution. The untreated and PEO coated AZ31 magnesium alloy specimens were found to be susceptible to SCC, despite the fact that the PEO coatings offered an excellent general corrosion resistance. The results of the polarisation tests on the untreated AZ31 alloy specimen after prolonged immersion in ASTM D1384 electrolyte suggested the formation of a film on the surface constituted by the corrosion products. The cracking of this film and the evolution/ingress of hydrogen at these defective sites during the SSRT tests in the corrosive environment was believed to be responsible for the SCC of the untreated alloy. Similarly, the cracking of the PEO coatings during the SSRT test, the consequent exposure of the underneath magnesium alloy substrate and the associated electrochemical reactions were attributed as reasons for the SCC of the PEO coated specimens. The transgranular mode of fracture in all the cases avowed that the hydrogen induced cracking was the mechanism of SCC.     

Comparison of testing solutions on the protection of Al-alloys using a Mg-rich primer

Magnesium-rich coatings present a new and challenging field of development for the corrosion protection of aluminium structures. These coatings are capable of sacrificial protection, but assessment of their efficiency and durability can be strongly affected by the testing environment. In this work two solutions commonly used in our studies are compared: 0.1% NaCl and dilute Harrison solution (DHS). The corrosion behaviour of two aluminium alloys coated with a magnesium-rich coating, of pure magnesium and of the bare aluminium substrates was assessed in the two solutions using electrochemical techniques. The corrosion rate of pure magnesium was higher in DHS, although the dissolution rate of the magnesium embedded in the polymer matrix was not significantly affected. The impedance spectra of the scribed samples resembled that of the bare substrates in NaCl solution but not in DHS.     

Corrosion resistance of WE43 and AZ91D magnesium alloys with phosphate PEO coatings

The corrosion performance of WE43-T6 and AZ91D magnesium alloys with and without treatment by plasma electrolytic oxidation (PEO) was investigated by electrochemical measurements in 3.5 wt.% NaCl solution. For untreated WE43-T6 alloy, formation of a uniform corrosion layer (Mg(OH)₂) was accompanied by initial pits around magnesium-rare earth intermetallic compounds. The AZ91D alloy disclosed increased corrosion susceptibility, with localized corrosion around the β-phase, though the β-phase network phase acted as a barrier for corrosion progression. PEO treatment in alkaline phosphate electrolyte improved the corrosion resistance of WE43-T6 alloy only at the initial stages of immersion in the test solution. However, PEO-treated AZ91D alloy revealed a relatively high corrosion resistance for much increased immersion times, contrary to the relative corrosion resistances of the untreated alloys. The improved performance of the PEO-treated AZ91D alloy appears to be related to the formation of a more compact coating.     

Structure and formation mechanism of phosphate conversion coating on die-cast AZ91D magnesium alloy

Phosphate conversion coating, which is considered as an alternative to chromium conversion coating for improving the corrosion resistance of die-cast AZ91D magnesium alloy is studied. The structure and formation mechanism of the coating was investigated in details using ESEM/EDX, XRD, EPMA, ICP and electrochemical method. It was found that the conversion coating was composed of complex phosphate containing magnesium and aluminum and showed amorphous structure. The thickness of the coating was about 10 μm. A possible formation mechanism for phosphate conversion coating was proposed. Local pH rise due to the evolution of hydrogen in the vicinity of micro-cathode attributed to the movement of hydrolysis reaction balance for manganese dihydro phosphate in treating solution and resulted in the phosphate coating precipitated on metal surface. Initial depositing position was related to the microstructure of substrate. Galvanic effect between α phase and β phase caused the flower-like phosphate nuclei preferential depositing on β phase. Ball-like phosphate nuclei deposited mainly in α phase interior due to the micro-galvanic effect within α phase. The primary α phase was removed from the metal matrix due to the corrosion dissolution, which suggested the anodic dissolution mechanism during phosphate conversion coating growth. The inner stress in dried film resulted in random distribution of the network micro-cracks on film surface, the crack site did not correspond to β phase.     

镁合金阳极氧化膜在NaCl溶液中的腐蚀行为

利用盐水浸泡实验研究了AZ91D镁合金阳极氧化膜层在3．5％NaCl溶液中的腐蚀行为。结果表明：AZ91D镁合金阳极氧化膜层不论封闭与否,在中性NaCl溶液中浸泡出现第一个腐蚀点后,膜层表面均很少再出现新的腐蚀点,而是原有的腐蚀点向纵、横两个方向扩展形成腐蚀坑,表面呈“树枝”状腐蚀形貌;浸泡溶液的pH值对阳极氧化膜层的耐蚀性影响很大,酸性溶液中的腐蚀速率明显大于中、碱性溶液的;随浸泡溶液温度的升高阳极氧化膜层的腐蚀速率加快。据此,提出了AZ91D镁合金阳极氧化膜层在NaCl溶液中腐蚀过程的模型。     

Corrosion properties of steel protected by nanometre-thick oxide coatings

A comprehensive study of the corrosion properties of low alloy steel protected by 40–50 nm aluminium and tantalum mixed oxide coatings grown by atomic layer deposition is reported. Electrochemical and surface analysis was performed to address the effect of substrate surface finish and whether an oxide mixture or nanolaminate was used. There was no dissolution or breakdown for nanolaminate alumina/tantala stacks in acidic NaCl solution. Localised corrosion (pitting) took place when defects exposing the substrate pre-existed in the coating. Substrate pre-treatment by brushing and H₂–Ar plasma was instrumental to block or slow down pit initiation by reducing the defect dimensions.     

Localized coating failure of epoxy-coated aluminium alloy 2024-T3 in 0.5 M NaCl solutions: Correlation between coating degradation, blister formation and local chemistry within blisters

The role of pH on the nature and rate of the degradation of epoxy coatings on AA2024-T3 panels and subsequent corrosion of the substrate during immersion in NaCl solutions was investigated. In acidic solutions both blister formation and growth are rapid. Blisters become very large (≈1 cm) and new blisters appear to form for a certain time after exposure. Often very small (∼0.1 mm) clear blisters surround these large blisters. Enhanced blister formation is due to irreversibly increased permeability of the coating for chloride ions and protons, the formation of more defect sites within the coating, and the weakening/dissolution of the oxide layer in low pH environments. In neutral pH solutions, coatings fail by forming one, or at most two, active blisters (red in color) within a few days of immersion with the time-to-failure dependent upon coating quality and thickness. Blister growth is a very slow process, and blister diameters rarely exceed a few millimeters even after several weeks. The accumulation of corrosion product within the blister slows down the corrosion rate and blister growth. The chloride concentration in the occluded solutions within the blister is significantly increased over the bulk concentration, and the pH is often in the acidic range. From electrochemical measurements it can be concluded that the anodic and cathodic reactions are confined to the blister and its immediate surroundings, rather than involving more of the surface over which the coating is intact. Based on corrosion morphology it is concluded that replated copper contributes to the overall cathodic reaction.     

AZ61A镁合金搅拌摩擦焊接头在NaCl溶液中的腐蚀行为(英文)

对6mm厚的挤压态AZ61A镁合金板进行搅拌摩擦对接焊。采用浸泡试验研究焊接接头在NaCl溶液中的腐蚀行为,建立了一个经验公式来预测在不同的溶液pH值、浸泡时间和氯离子浓度下的接头腐蚀速率。该经验公式的可信度水平为95%。采用3因素、5水平的中央复合旋转设计方法来减少实验工作量。采用响应面方法来构建方程。结果表明,在碱性溶液中AZ61A镁合金接头的腐蚀速率要比其在酸性或中性溶液中的低,而且腐蚀速率随着氯离子浓度的降低和浸泡时间的延长而减少。β相的分布对其腐蚀形貌有重要影响。     

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.