Corrosion of hot extrusion AZ91 magnesium alloy. Part II: Effect of rare earth element neodymium (Nd) on the corrosion behavior of extruded alloy

The corrosion behavior of extruded Nd-free AZ91 and extruded AZ91 + 1.5Nd alloy was investigated by weight loss and electrochemical measurements. The results showed that the extruded AZ91 + 1.5Nd alloy had higher corrosion resistance compared to the extruded Nd-free AZ91 alloy, which could been explained from point of view of microstructure changes: (1) the significant decrease of twins and dislocation decreased the anodic dissolution rate; (2) the micro-galvanic corrosion was inhibited by the formation of Al₃Nd phase; and (3) Nd not only increased the percent of Non-Faraday process, but also led to anisotropic feature on the corrosion mechanism.     

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.     

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.     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.     

Effect of excimer laser surface melting on the microstructure and corrosion performance of the die cast AZ91D magnesium alloy

Excimer laser surface melting (LSM) of the die cast AZ91D alloy has been investigated in terms of microstructure and corrosion behaviour. Excimer LSM of the alloy resulted in a highly homogeneous and refined melted microstructure, which improved the corrosion resistance of the alloy. The latter was associated with the large dissolution of intermetallic phases and the enrichment of aluminium within the melted layer. An increased number of laser pulses resulted in thicker melted layers, but also in enhanced porosity and the formation of micro-cracks at the overlapping area. Both factors diminished the corrosion resistance of the laser-treated alloy.     

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。     

复配缓蚀剂在50%乙二醇冷却液中对AZ91D镁合金的缓蚀作用

采用电化学试验、表面形貌观察、腐蚀产物分析等方法研究了磷酸氢二钠(DSP)和D-葡糖酸钠(GS)两种物质复配后对镁合金在50%(体积分数,下同)乙二醇型冷却液中的缓蚀作用。结果表明:DSP对AZ91D镁合金在50%乙二醇冷却液中是一种混合抑制型缓蚀剂,GS对AZ91D镁合金在50%乙二醇冷却液中没有缓蚀作用;DSP和GS之间存在缓蚀协同效应,复配后的缓蚀剂是一种以抑制阳极过程为主的混合型缓蚀剂;GS的添加量存在极值,而DSP和GS的质量浓度比达到4∶1时,即复配缓蚀剂E,其缓蚀率趋于稳定;随着复配缓蚀剂E加入量的增大,缓蚀率增大,其加入量为2.5g/L时,缓蚀率高达90%以上;复配缓蚀剂E对AZ91D镁合金起到缓蚀作用主要表现为形成了MgHPO4沉淀物,通过GS络合在镁合金表面,从而抑制了镁合金在乙二醇冷却液中的腐蚀。     

In situ observation of formation and spreading of micro-droplets on magnesium and its alloy under cyclic wet-dry conditions

The formation and spreading of micro-droplets on pure magnesium and its alloy in an atmosphere of water vapor under cyclic wet-dry conditions was studied using an environmental scanning electron microscope (ESEM). The in situ observations indicated that the corrosion product stimulated the formation and spreading of micro-droplets, and the grain boundaries for pure magnesium and β phase for AZ91 magnesium alloy had no influences on this process. The oxygen concentration on the surface generally increased with the wetting time. The corrosion products decreased the corrosion rate.     

Influence of chloride ion concentration and temperature on the corrosion of Mg-Al alloys in salt fog

The influence of temperature and chloride concentration on the corrosion behaviour of Mg-Al alloys exposed to salt fog was evaluated. Corrosion attack increased with decreasing aluminium content in the alloy and increasing Cl⁻ concentration and temperature. The effect of Al-Mn inclusions, which revealed several stoichiometries and were up to 300 mV more noble than the magnesium matrix, was only noticeable in the early stages of corrosion of the AZ31 alloy. Aluminium segregation and β-phase distribution were the main controlling factors for the AZ80 and AZ91D alloys, the latter being more susceptible to variations in the saline concentration.     

AZ91D镁合金在NaCl溶液中腐蚀过程的电化学噪声分析

通过电化学噪声技术（EN）、小波变换（WT）、噪声电阻（Rn）和功率谱密度(PSD)等方法研究了AZ91D镁合金在碱性含氯溶液中的腐蚀行为.结果表明,AZ91D镁合金在碱性含氯溶液中的腐蚀过程可以分为三个不同的腐蚀阶段：伴随氢气泡产生、吸附和脱附的阳极溶解阶段,点蚀发展阶段和最后形成MgH2保护膜的腐蚀抑制阶段.     

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.     

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。     

About some corrosion mechanisms of AZ91D magnesium alloy

The present work is dedicated to a study of the corrosion resistance of AZ91D (91% Mg) alloy in wet environments. Three industrial alloys obtained by die-casting or sand casting were subjected to salt spray corrosion tests (ASTM-B117 standard) and immersion tests. Weight loss kinetic curves were measured. Surface analysis was performed by X-ray photoelectron diffraction (XPS). After corrosion the sand cast alloy presents a surface mainly enriched in hydroxides and carbonates while the die-cast alloy presents a surface enriched also in mixed Mg-Al oxides. The quantitative analysis of the rate Mg/Al shows an enrichment in aluminium for the die-cast alloys in comparison to the sand cast alloy.     

Effect of heat treatment on corrosion behaviour of magnesium alloy AZ91D in simulated body fluid

The research explored ways of improving corrosion behaviour of AZ91D magnesium alloy through heat treatment for degradable biocompatible implant application. Corrosion resistance of heat-treated samples is studied in simulated body fluid at 37 °C using immersion and electrochemical testing. Heat treatment significantly affected microgalvanic corrosion behaviour between cathodic β-Mg₁₇Al₁₂ phase and anodic α-Mg matrix. In T4 microstructure, dissolution of the β-Mg₁₇Al₁₂ phase decreased the cathode-to-anode area ratio, leading to accelerated corrosion of α-Mg matrix. Fine β-Mg₁₇Al₁₂ precipitates in T6 microstructure facilitated intergranular corrosion and pitting, but the rate of corrosion was less than those of as-cast and T4 microstructures.     

Influence of surface pretreatment on the anodizing film of Mg alloy and the mechanism of the ultrasound during the pretreatment

The effect of surface pretreatments on the micro-morphology, composition and the corrosion resistance of the anodic films formed on AZ91D magnesium alloys was investigated. The results showed that the aluminium content increased layer can be formed on the surface of the AZ91D magnesium alloys by the immersion pretreatment in aluminium nitrate solution with or without ultrasound. The pretreated surface with ultrasound was more uniform except for some pits. The anodic oxidation films on the pretreated magnesium alloys with ultrasound contained more aluminium and the pretreatment improved the uniformity of the anodic films. The use of ultrasound in the pretreatment process could significantly decrease the quantity and size of the micro-pores on the anodic films. The corrosion resistance of the anodic films formed on the pretreated magnesium alloys was improved. The corrosion resistance with ultrasound was better than that without ultrasound in the pretreatment process. In this paper, the effect and mechanism of the ultrasound during the immersion pretreatment process in aluminium nitrate solution was also discussed.     

Study of the corrosion inhibition effect of sodium silicate on AZ91D magnesium alloy

The poor corrosion resistance of magnesium alloys is a major impediment to their applications in many fields. In this paper, sodium silicate as a corrosion inhibitor is studied on the inhibition effect of AZ91D magnesium alloy. From the results of the corrosion tests, sodium silicate could effectively improve the corrosion resistance of alloy at the optimum concentration 10 mmol/L, while the pH value range from 10.5 to 12.5 is preferable. The corrosion inhibition mechanism of the protective layers is also discussed. These results can provide a guide for the protection of magnesium alloy in the cooling water systems, etc.     

AZ91D镁合金电偶腐蚀的扫描Kelvin探针研究

利用扫描Kelvin探针技术(SKP)研究AZ91D镁合金与316L不锈钢偶接件在盐雾试验中电偶腐蚀规律。通过在中性盐雾试验不同周期的表面腐蚀形貌的观察和伏打电位分布图的测量结果分析表明,AZ91D镁合金电偶腐蚀效应与偶接阴阳极的伏打电位差密切相关,AZ91D镁合金与316L不锈钢偶接件存在较大的电位差(约为–1.28V),其电偶腐蚀效应非常显著。在盐雾试验初始阶段,腐蚀主要发生在偶接界面AZ91D镁合金一侧,该腐蚀区域的伏打电位增加幅度较大,而316L不锈钢受到保护没有发生明显腐蚀。随着盐雾试验时间的延长,AZ91D镁合金腐蚀加快,腐蚀产物覆盖区域不断扩大,24h盐雾试验后,偶接件的平均伏打单位差由原始的–1.29V增加到–1.53V,AZ91D镁合金的电偶腐蚀效应加大。由于AZ91D镁合金在盐雾中生成的腐蚀产物对基体具有一定的保护作用,当腐蚀产物不断增加并覆盖表面,偶接件的电位差减小导致AZ91D镁合金的电偶腐蚀效应降低。     

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.     

Electrochemical behaviour of the Mg alloy AZ91D in borate solutions

Corrosion and passivation behaviour of Mg-based alloy AZ91D was investigated in aqueous sodium borate solutions (pH 9.2) in relation to some test parameters, using electrochemical techniques. Increasing borate concentration (0.01–0.10 M) or temperature up to 298 K leads to increase the corrosion rate of the alloy. However, at temperatures higher than 298 K borate anions have stronger propensity to passivate the alloy, thereby decreases its corrosion rate. For a fixed borate concentration increasing Cl⁻ addition is correlated with a more negative corrosion potential and a higher corrosion rate, as well as increase the vulnerability of the anodic passive film for breakdown. The influence of oxidizing potentials over the range −1.5 V to 2.75 V (SCE) on the performance of the alloy in the most aggressive borate solution (0.10 M) reveals that higher potentials, induces better passivation due to formation of a rather thick and more protective n-type semiconducting film. A modified Randles circuit including Warburg impedance to account for the diffusion of reactants or products through the surface film was adopted to analyse the EIS data, that gave impedance parameters in good agreement with the results of open circuit potential and dc polarization measurements.