The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D ≈ AM60 ≈ MEZ ? AZ91D-DC ? AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier.     

钇对压铸AZ91镁合金耐腐蚀性能的影响

研究了在中性NaCl水溶液中压铸AZ91及AZ91 1%Y合金的腐蚀性能.结果表明,在相同浓度及相同温度的NaCl腐蚀介质中,压铸AZ91 1%Y合金的腐蚀速率明显低于AZ91合金.对压铸AZ91及AZ91 1%Y镁合金腐蚀层中各元素的XPS分析结果表明,AZ91 1%Y合金腐蚀试样中存在Y的氧化物,可以起到钝化保护膜的作用,从而提高了镁合金的耐腐蚀性能.     

AZ91D镁合金电偶腐蚀的研究

在自来水和3.5%NaCl溶液中测试了铸造AZ91D镁合金与铝合金、锌合金、Q235碳钢和Cu偶合后的电偶腐蚀行为,研究了腐蚀环境、偶接材料和阴阳极面积比(CAAR)对铸造AZ91D镁合金电偶腐蚀行为的影响。在电偶腐蚀过程中测量溶液的pH值以及电偶腐蚀电流;用失重法计算了铸造AZ91D镁合金的电偶腐蚀速率,利用SEM观察了AZ91D镁合金的腐蚀形貌,并对腐蚀产物进行XRD分析。结果表明,AZ91D镁合金在电偶腐蚀过程中会使溶液的pH值升高,并伴有以Mg(OH)₂为主的腐蚀产物的生成;溶液中Cl^-的存在会加速AZ91D镁合金的电偶腐蚀速率;低氢过电位金属Q235碳钢和Cu对AZ91D镁合金的电偶腐蚀加速效果明显高于中氢过电位金属铝合金和锌合金,偶接材料的极化性能对AZ91D镁合金的电偶腐蚀速率有较大影响。同时,大的阴阳极面积比会加速AZ91D镁合金的电偶腐蚀速率,且AZ91D镁合金的电偶腐蚀电流随阴阳极面积比的增大而呈线性增长趋势。     

Comparison of corrosion behaviors of AZ31, AZ91, AM60 and ZK60 magnesium alloys

The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corrosion resistance of the four materials is ranked as ZK60＞AM60＞AZ31＞AZ91. The corrosion processes of the four magnesium alloys were also analyzed by SEM and energy dispersive spectroscopy(EDS). The results show that the corrosion patterns of the four alloys are localized corrosion and the galvanic couples formed by the second phase particles and the matrix are the main source of the localized corrosion of magnesium alloys. The corrosion resistance of the different magnesium alloys has direct relationship with the concentration of alloying elements and microstructure of magnesium alloys. The ratio of the β phase in AZ91 is higher than that in AZ31 and the β phase can form micro-galvanic cell with the alloy matrix, as a result, the corrosion resistance of AZ31 will be higher than AZ91. The manganese element in AM60 magnesium alloy can form the second phase particle of AlMnFe, which can reduce the Fe content in magnesium alloy matrix, purifying the microstructure of alloy, as a result, the corrosion resistance of AM60 is improved. However, due to the more noble galvanic couples of AlMnFe and matrix, the microscopic corrosion morphology of AM60 is more localized. The zirconium element in ZK60 magnesium alloy can refine grain, form stable compounds with Fe and Si, and purify the composition of alloy, which results in the good corrosion resistance of ZK60 magnesium alloy.     

镁及镁合金在NaCl水溶液中的腐蚀行为

研究了纯Mg、AZ31和AZ91D镁合金在pH=12,浓度为5%的NaCl溶液中的腐蚀行为,从腐蚀形貌和腐蚀速率等方面对其进行了定性和定量描述,并对其腐蚀杌理进行了探讨.随着腐蚀时间的延长,纯Mg,AZ31和AZ91D镁合金的腐蚀速率呈现出先急剧减小再缓慢降低,最后达到一个稳定值的趋势.同时,随着合金中Al含量的提高,镁合金腐蚀速率降低,因此AZ91D镁合金表现出比AZ31镁合金更好的耐腐蚀性能.     

AZ91D镁合金手汗腐蚀机理研究 I.手汗模拟液中AZ91 D镁合金腐蚀的动力学规律

通过建立简易气体收集装置 ,研究了手汗液中不同组分对AZ91D合金的侵蚀性以及对合金表面析氢动力学过程的影响规律 .发现手汗液各成分对镁合金的腐蚀具有不同的侵蚀作用 ,其中尿素对镁合金的腐蚀具有一定的缓蚀作用 ,而乳酸和NaCl则是较强的侵蚀性介质 ,且当乳酸与NaCl共存时 ,具有最强的侵蚀性 .各成分单独存在时 ,合金表面析氢动力学过程满足不同的函数关系 ,在纯水和尿素体系 ,满足logistic关系式 ;在乳酸和NaCl体系 ,满足多项式关系 .手汗液各成分对合金的不同侵蚀作用规律是导致动力学曲线不同的主要原因 .     

微弧氧化处理对AZ91D镁合金腐蚀行为的影响

采用碱性硅酸盐溶液,在AZ91D镁合金试样表面制得微弧氧化膜,并利用电化学阻抗方法对镁合金及微弧氧化处理试样在3.5%NaCl溶液中的腐蚀行为进行比较研究.结果表明,镁合金经微弧氧化处理后,腐蚀电位和膜层阻抗均有一定程度的提高.但在浸泡过程中,微弧氧化处理试样的电化学参数呈现出不同的变化规律,初期波动较大,后期则逐渐降低,趋向稳定.     

Studies on magnesium and its alloys in battery electrolytes

Abstract

Studies on the anode efficiency of magnesium and its alloys in battery electrolytes such as magnesium perchlorate, magnesium bromide, and magnesium chloride solutions were made by galvanostatic polarisation and corrosion rate measurements. The open circuit potential and corrosion rate of magnesium increase when lead is present in the alloy. The corrosion rates were observed to follow the order Mg> AP65 (Mg?(6·0?7·0) Al?(4·4?S·0)Pb) > AZ61(Mg?(5·8?7·2)Al?(0·5?1·5)Zn) > AZ31(Mg?(2·5?3·5)Al?(0·6?1·4)Zn) in all three electrolytes. Anode efficiency increased with increasing current density up to 40 mA cm^?2, but decreased above this level. Galvanostatic polarisation results indicated that corrosion of magnesium and its alloys in these electrolytes occurs under cathodic control. Of the tested alloys, AZ31 and AZ61 were found to be most suitable in respect of corrosion rate and anode efficiency in 2M Mg(ClO₄)₂ solution.     

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     

Effect of magnesium hydride on the corrosion behavior of an AZ91 magnesium alloy in sodium chloride solution

The effect of magnesium hydride on the corrosion behavior of an as-cast AZ91 alloy in 3.5 wt.% NaCl solution was investigated using gas collection method and potentiostatic test. The Pourbaix diagram of Mg–H₂O system was built using thermodynamic calculation. It was possible that magnesium hydride could form in the whole pH range in theory. The experimental results showed that at cathodic region, magnesium hydride formed on surface, which was the controlling process for the corrosion behavior of AZ91 alloy; at anodic region and free corrosion potential, magnesium hydride model and partially protective film model, monovalent magnesium ion model and particle undermining model were responsible for the corrosion process of AZ91 alloy.     

The in vivo and in vitro corrosion of high-purity magnesium and magnesium alloys WZ21 and AZ91

Corrosion was studied in vitro in Nor’s solution (CO₂ – bicarbonate buffered Hank’s solution) at 37 °C, and in vivo implanted in the lower back muscle of rats. Nor’s solution is a good model for HP Mg and WZ21, because (i) the pH is maintained by the same buffer as in blood and (ii) concentrations of corrosive chloride ions, and other inorganic constituents, are similar to those in blood. The higher in vitro corrosion rate of AZ91 was caused by micro-galvanic from second phases. The lower in vivo corrosion rate of AZ91 was tentatively attributed to suppression of micro-galvanic corrosion by tissue encapsulation.     

Corrosion behaviour of pure Mg,AS31 and AZ91 in buffered and unbuffered sulphate and chloride solutions

Abstract

The low corrosion resistance of magnesium limited its application in industrial affairs. The main corrosive anions for magnesium are sulphate and chloride. This paper deals with their effect at low concentrations on the corrosion behaviour of Mg and Mg based alloy (AS31 and AZ91) in presence/absence of buffer solutions (pH 8). The electrochemical measurements used are open circuit potential and potentiodynamic polarisation. The results exposed that in the absence of a protective layer, general corrosion is observed to occur at greater rate than when sulphate is present; however, the general corrosion is transformed to localised corrosion faster in presence of chloride. In the presence of a protective layer, the localised corrosion is perceived in the case of chloride more than sulphate. The presence of aluminium in the alloys has two contradictory actions. One increases the passivity of the formed layer and the other increases the localised corrosion. The percentage of aluminium in the alloy controls these actions.     

Direct electroless nickel–boron plating on AZ91D magnesium alloy

A Ni–B coating was electroless-deposited directly on acetic acid pickled AZ91D. The plating rate was found to be influenced by pH, temperature, and bath composition. The electroless Ni–B plating exhibits a uniform surface and an amorphous structure. Polarization curve and electrochemical impedance spectroscopy measurements in 3.5 wt.% sodium chloride aqueous solution suggest that the plating can protect the magnesium alloy substrate from corrosion attack. It is proposed that different deposition reactions dominate in different stages of the plating process.     

AZ91镁合金表面电化学沉积羟基磷灰石涂层的制备及其耐蚀性

采用电化学沉积方法在AZ91镁合金表面制备了羟基磷灰石(HA)涂层,研究了电沉积工艺参数对羟基磷灰石涂层形貌和相组成的影响,并通过腐蚀浸泡试验、极化曲线测试等方法对该涂层的耐蚀性进行了研究。结果表明:当溶液pH为4.5,温度为60℃时,涂层的致密性最好,呈放射状的结构,主要成分为HA相,涂层的厚度约为60~70μm,与基体结合较好;HA涂层对镁合金基体具有较好的保护作用,显著提高了基体合金在生理溶液中的耐蚀性。     

汽车发动机冷却液中镁合金缓蚀剂的研究

采用XRD、电化学极化曲线、化学浸泡等实验方法，研究了腐蚀性水体系中单种无机盐、复配无机盐缓蚀剂对AZ91D镁合金的缓蚀作用，并用正交优化设计确定了Na2MoO4+Na2SiO3+KMnO4复配无机盐缓蚀剂的优化配方；研究了水-乙二醇（1：1）防冻液基础液体系中缓蚀剂对AZ91D镁合金的缓蚀作用.结果表明，在腐蚀性水中KMnO4、Na3PO4、Na2MoO4和NaF对AZ91D镁合金有一定的缓蚀作用，Na2B4O7不具有缓蚀作用，有可能加速其腐蚀；复配Na3PO4+KMnO4及Na2MoO4+Na2SiO3+KMnO4对AZ91D镁合金腐蚀有缓蚀作用，而Na3PO4+Na2B4O7会加速其腐蚀.在水-乙二醇体系中，Na2S对AZ91D镁合金腐蚀有较好的缓蚀作用；确定了2种适用于水-乙二醇中的有机-无机复合缓蚀剂配方，缓蚀效率分别为98.1％和94.3％.     

Corrosion performance of magnesium alloys MEZ and AZ91

The corrosion performance of sand cast MEZ_S, zirconium-grain-refined MEZ_R, sand cast AZ91_S, and high pressure diecast AZ91_D magnesium alloys were evaluated by means of salt spray testing, optical metallography, hydrogen evolution, polarisation curve measurement and AC impedance spectroscopy. The results show that the corrosion resistance of the four alloys can be ranked in decreasing order as AZ91_D > AZ91_S ≈ MEZ_R > MEZ_S and that the intergranular phases and chemical composition of the matrix phase have a significant influence on the corrosion performance. Alloys with a finer grain size and higher aluminum or zirconium contents exhibit better corrosion resistance.     

Influence of chemical composition on corrosion resistanceof AZ91D magnesium alloy ingots

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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。     

Corrosion performance of laser-remelted Al-Si coating on magnesium alloy AZ91D

Laser remelting was applied to plasma-sprayed Al-Si coating on magnesium alloy AZ91D to improve corrosion performance. Both salt spray testing and potentiodynamic polarization measurement in 3.5% NaCl solution indicated that laser-remelted Al-Si coating acquired better corrosion resistance than AZ91D and plasma-sprayed Al-Si coating. The decreasing order of the corrosion rates are AZ91D base metal, sprayed Al-Si coating and laser-remelted Al-Si coating. The fine Al-Si eutectic matrix in the laser-remelted microstructure contributed to the improved corrosion performance relative to the AZ91D and the plasma-sprayed coating. The predominant corrosion mechanisms in AZ91D, plasma-sprayed coating and laser-remelted coating are intra-granular corrosion, crevice corrosion and the combined pitting and galvanic corrosion, respectively.