General and localized corrosion of magnesium alloys: A critical review

Magnesium (Mg) alloys as well as experimental alloys are emerging as light structural materials for current, new, and innovative applications. This paper describes the influence of the alloying elements and the different casting processes on the microstructure and performance of these alloys and corrosion. It gives a comprehensible approach for the resistance of these alloys to general, localized and metallurgically influenced corrosion, which are the main challenges for their use. Exposure to humid air with ∼65% relative humidity during 4 days gives 100–150 nm thickness. The film is amorphous and has an oxidation rate less than 0.01 μm/y. The pH values between 8.5 and 11.5 correspond to a relatively protective oxide or hydroxide film; however above 11.5 a passive stable layer is observed. The poor corrosion resistance of many Mg alloys can be due to the internal galvanic corrosion caused by second phases or impurities. Agitation or any other means of destroying or preventing the formation of a protective film leads to increasing corrosion kinetics. The pH changes during pitting corrosion can come from two different reduction reactions: reduction of dissolved oxygen (O) and that of hydrogen (H) ions. Filiform corrosion was observed in the uncoated AZ31, while general corrosion mainly occurred in some deposition coated alloys. Crevice corrosion can probably be initiated due to the hydrolysis reaction. Exfoliation can be considered as a type of intergranular attack, and this is observed in unalloyed Mg above a critical chloride concentration.     

基于专利文献的镁合金腐蚀与防护技术的最新进展(英文)

对镁合金腐蚀与防护的国内外相关专利文献进行分析,总结最新的表面防护技术,包括转化膜、电镀、表面涂层和多种复合处理技术,此外还介绍一些新的处理技术。发现转化膜技术在所有专利文献中占有极大的比例,说明在实际的工业应用中转化膜技术非常重要,且占主导地位。由于镁合金零部件形状和使用特性的多样性,单一的表面技术难以满足性能所需,越来越多的复合表面处理技术、环保型的新技术被发明用来进行镁合金的防护处理。此外,专利技术的投资成本、操作的难易程度、涂层的性能等因素极大地影响该专利技术的工业应用。     

Effects of electric parameters on corrosion resistance of anodic coatings formed on magnesium alloys

Anodic coatings were obtained by micro-arc oxidation on AZ91HP magnesium alloys in a solution containing 10 g/L NaOH and 8 g/L phytic acid. The effects of electric parameters including frequency, final voltage, duty cycle and current density on the corrosion resistance of anodic coatings formed on the magnesium alloys were investigated by using an orthogonal experiment of four factors with three levels. The results show that the final voltage plays a main role on the coating properties. The orders of affecting corrosion resistance and coating thickness are separately ranked from high to low as, final voltage>duty cycle>current density>frequency and final voltage>current density>frequency>duty cycle. The final voltage influences the corrosion resistance of the anodized samples mainly by changing the surface morphology and coating thickness.     

Corrosion behavior of 3C magnesium alloys in simulated sweat solution

AZ series Mg alloys AZ31, AZ61, and AZ80 are widely applied in 3C (computer, communication, and consumer electronic) industry. Their corrosion characters in simulated sweat solution have been investigated by electrochemical technology, surface analysis, and pH measurements. Electrochemical test results showed that the three magnesium alloys revealed different corrosion resistance (R_t) in simulated sweat solution, R_t(AZ31) < R_t(AZ61) < R_t(AZ80). Three major components of simulated sweat solution played different roles during corrosion processes. Lactic acid was a kind of strong erosive medium for the magnesium alloys, and NaCl can induce pitting corrosion on alloys surface, while urea acted as a corrosion inhibitor. The corroded surface morphology of the three magnesium alloys was observed using scanning electron microscopy (SEM) and corrosion products were analyzed by X‐ray diffraction (XRD). Result of pH measurement tests showed that there were differences in climbing speed and final values of pH for the three magnesium alloys in simulated sweat solution.     

Corrosion behavior of magnesium and magnesium alloys

The automotive industry has crossed the threshold from using magnesium alloys in interior applications such as instrument panels and steering wheels to unprotected environment such as oil pan, cylinder head and wheels. The expanding territory of magnesium leads to new challenges.mainly environmental degradation of the alloys used and how they can be protected. The present critical review is aimed at understanding the corrosion behavior of magnesium and magnesium alloys in industrial and marine environments, and the effect of microstructure, additive elements and inhibitors on the corrosion mechanism.     

Investigations of the aqueous corrosion of pretreated magnesium alloys by means of electrochemical noise measurements

An important possibility to improve the corrosion behaviour of magnesium alloys is the application of protective coatings. The quality of such coatings depends mainly on the pretreatment and the exposure conditions after pretreatment. Since magnesium surfaces change much faster under atmospheric conditions than those of almost any other technical material, it is necessary to pay special attention to this particular feature. The activity of acid‐pickled surfaces of the magnesium alloys AZ31 and AZ91 in dependence on the exposure time and the humidity conditions was investigated with electrochemical noise (EN) measurements. In addition to pickling, plasma chemical vapour deposition processes open new possibilities for an economical, as well as ecologically quite safe, pretreatment. The results of EN investigations after acid pickling as well as specific plasma oxidation treatments of the two magnesium alloys after exposure to air with different humidities are presented.     

Corrosion and electrochemical behavior ofAZ31D magnesium alloys in sodium chloride

The corrosion and electrochemical behavior of extruded AZ31D magnesium alloys in NaCl solution were investigated using SEM, XRD and electrochemical method. It is found that AZ31D is susceptive to Cl^- ion, and the open circuit potential shifts to more negative values with increasing chloride concentration. Pitting occurs at corrosion potential and corrosion area enlarges with enhanced polarization. Tafel slopes of the cathode branches in different testing solution are almost the same. Cl^- concentration affects cathode course slightly. High frequency capacitive loops shrink with the increase of Cl^- concentration. Corrosion initiates from the grain boundary and spreads to entire surface with time.     

固溶处理态Mg-Nd-Gd-Sr-Zn-Zr生物镁合金的组织与均匀腐蚀行为

对Mg-(4-x)Nd-xGd-0.3Sr-0.2Zn-0.4Zr(质量分数,%,x=0, 1和3)镁合金进行了固溶处理。采用扫描电镜、能谱分析仪和X射线衍射仪研究了合金的显微组织与物相。利用失重和析氢法测试了合金在模拟体液中的腐蚀速率,并观察了合金的腐蚀形貌。结果表明,含1%Gd的合金晶粒最细小,且第二相较为连续地分布在基体周围,腐蚀速率也最低;而含3%Gd的合金晶粒最粗大,腐蚀速率最快。3种合金的腐蚀形貌较为均匀,是理想的生物可降解材料。     

汽车用AZ91镁合金的耐腐蚀性能

以AZ91镁合金为研究对象,研究了NaCl溶液的浓度、腐蚀时间、温度和搅拌速度对AZ91镁合金耐腐蚀性的影响。利用扫描电镜观察了腐蚀后的表面形貌和横截面形貌,定性分析了AZ91镁合金在NaCl溶液中的腐蚀行为。结果表明,随NaCl溶液浓度、腐蚀时间、温度和搅拌速度增加,AZ91镁合金腐蚀速率主要呈递增趋势,且腐蚀形式为沿晶腐蚀。     

镁合金大气电偶腐蚀初期规律

研究了AZ91D、AM50、AM60铸造镁合金与A3钢、316L不锈钢、H62黄铜、LY12铝合金组成的电偶对分别在青岛和武汉现场暴晒3个月和6个月后的大气电偶腐蚀行为及规律.结果显示, 镁合金始终是电偶对的阳极; 当其与其它4种材料偶接时, 其腐蚀速率增加.镁合金与A3钢偶合后, 其大气电偶腐蚀效应最大, 而与LY12铝合金组成的电偶对的大气电偶腐蚀效应最小.不同镁合金的大气电偶腐蚀效应存在如下关系: γAZ91D>γAM50>γAM60.暴晒3个月后, 青岛的大气电偶腐蚀效应明显高于武汉的大气电偶腐蚀效应.随着暴晒时间的延长, 青岛和武汉的大气电偶腐蚀效应分别呈降低和升高的趋势.     

Formation and properties of stannate conversion coatings on AZ61 magnesium alloys

The effects of solution composition and temperature on the microstructure and corrosion resistance of stannate conversion coatings on AZ61 magnesium alloys were investigated. The conversion coating consisted of a porous layer as under layer intimately contacted with the magnesium plate and a hemispherical particle layer as major overlay formed right on top of the porous layer. During the coalescence of the hemispherical particles to form a complete coating on the magnesium alloy, some sites of discontinuity inevitably left and determined the corrosion resistance of the coating evaluated using a salt spray test. Increasing bath stannate ion concentration and lowering bath pH increased the population density of the hemispherical particles whose size was accordingly reduced. The corrosion resistance of the conversion coating was improved with finer particles, which were preferably formed at less alkaline solution with higher stannate ion contents. Furthermore, the conditions favoring the formation of finer particles also reduced the immersion time necessary for producing the conversion coating with optimal corrosion resistance.     

Effect ofT4 and T6 treatment on corrosion oldie cast AZ91D magnesium alloys in 3.5% NaCl

The effect of heat treatment on microstructure and corrosion behavior of die-cast AZ91D magnesium alloys in 3.5% NaCl solution was investigated by SEM, EDX, XRD and electrochemical technique. It is found that the distribution of β phase influences the corrosion morphology. Corrosion occurs preferentially in primary a phase and presents pitting corrosion feature in die-cast AZ91D. ARer homogenization of T4 treatment, β phase dissolves in a phase and forms a single phase with a matrix, and the corrosion form turns to localized corrosion. The attack initiates at local site, expands towards deep direction and produces ＂digging effect＂. After artificial aging of T6 treatment, β phase is produced in abundance and provides a great deal of effective micro-cathode for anodic dissolution, and the corrosion form exhibits in general corrosion.     

Review of studies on corrosion of magnesium alloys

This review provided some recent progress of the research on corrosion mechanisms of magnesium and its alloys and a basis for follow-on research. Galvanic corrosion, pitting corrosion, intergranular corrosion （IGC）, filiform corrosion, crevice corrosion, stress corrosion cracking （SCC）, and corrosion fatigue （CF） were discussed. The influence of metallurgical factors such as alloying elements, microstructure and secondary phases, processing factors such as heat treatment and weld, and environmental factors including temperature, relative humidity, solution pH values and concentration on corrosion were discussed. In particular, a mechanism of pitting corrosion caused by AlMn particles was proposed. The corrosion properties of AZ91D weld material were investigated.     

稀土Gd对SLM成型Mg-Zn-Gd合金耐蚀性能研究

镁合金具有高比强度与良好的生物相容性,是一种理想的骨植入材料。因镁合金降解速率过快在临床应用中受到限制,通过SLM可对其合金化并改善耐蚀性能。利用SLM成型Mg-1Zn-xGd(x=0、0.25、0.5、1、2 wt%)合金,测试镁合金在模拟体液中浸泡72 h平均腐蚀速率变化趋势,采用SEM、EDS与TEM检测手段辅助分析腐蚀机理。实验结果表明,Gd含量对镁合金腐蚀速率影响显著,添加0~2 wt% Gd后镁合金降解速率呈先降低后升高趋势,在添加0.5 wt% Gd时镁合金具有最佳耐腐蚀性能。腐蚀反应产生的表面钝化膜能够一定程度减缓腐蚀的进行,添加过量Gd后沿晶界析出Mg₅Gd相增多加剧了镁合金腐蚀。     

Effects of rare earths on the microarc oxidation of a magnesium alloy

The effects of rare earths on the properties of the microarc oxidation（MAO） coating on a magnesium alloy were investigated by means of scanning electron microscopy（SEM）,energy dispersive X-ray spectroscopy（EDS）,and electrochemistry methods.The results show that a nice and compact MAO coating was successfully obtained when the magnesium alloy was treated in nitrate solutions as the pre-treatment of MAO.However,the MAO was not successfully completed for the silicate electrolytes with the addition of rare earths.After the magnesium alloy being treated by rare earth nitrate,the obtained MAO coating has advantages such as uniform distribution of thickness,improved corrosion resistance,and nice-uniform surface,as compared with the untreated magnesium alloy.In addition,the time of non-ESP,the voltage and current density of the MAO process obviously decrease.Cerium oxide doped on the surface of the magnesium alloy can significantly improve the corrosion resistance of the MAO coating and decrease the current density of the MAO process,as compared with lanthanum oxide,whereas the doped rare earths have no significant effect on the components of the MAO coating.