4种铸造镁合金在SBF溶液中的腐蚀行为研究

比较了ZK60、AM60、AZ31和AZ91D等4种铸造镁合金在SBF模拟体液中浸泡72 h的腐蚀性能。利用SEM观察了镁合金腐蚀后的显微形貌,根据失重法计算了镁合金的腐蚀速率,采用极化曲线和电化学阻抗方法进一步评价了镁合金的耐蚀性。研究表明,AZ91D合金腐蚀速率最低,并且呈均匀腐蚀。AZ31合金耐蚀性最差,且点蚀严重,AM60和ZK60合金的耐蚀性相近。     

AZ91D镁合金微弧氧化膜在不同浓度NaCl溶液中的腐蚀行为(英文)

采用微弧氧化技术(MAO)在镁合金 AZ91D 表面制备微弧氧化陶瓷膜。利用电化学技术和浸泡实验研究该镁合金试样在不同浓度(0.1%,0.5%,1.0%,3.5%和 5.0%,质量分数) NaCl 溶液中的腐蚀行为。结果表明,试样的腐蚀速率随着氯离子浓度的升高而增大。在较高浓度(1.0%,3.5%和 5.0%)的 NaCl 溶液中的主要腐蚀形式是点蚀,而在较低浓度(0.1%和 0.5%)中是全面腐蚀。腐蚀过程可以分为两个阶段:亚稳态蚀点的出现和蚀点的生长。根据腐蚀过程中阻抗谱的特点,对镁合金微弧氧化膜试样在不同浓度 NaCl 溶液中浸泡 120 h 提出了不同的等效电路来模拟其腐蚀行为。     

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。     

Influence of rare earth element Ce and La addition on corrosion behavior of AZ91 magnesium alloy

Two types of AZ91 magnesium alloys containing rare earth element Ce or La were fabricated. Hydrogen evolution and electrochemical tests were carried out to evaluate the corrosion behavior of new AZRE (RE = Ce or La) and AZ91 alloys in 3.5% NaCl solutions (pH 6.50). Various corrosion rate tests indicated that addition of RE obviously enhanced corrosion resistance of AZ91 magnesium alloy. The optimal content of RE was 0.92% for Ce and 0.66% for La. Scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and low‐angle X‐ray diffraction (XRD) were used to characterize the effect of RE addition on microstructure and corrosion product film of AZ91 magnesium alloy. The refined β phase and formation of γ phase in AZRE alloy were observed by SEM, which resulted in the improvement of corrosion resistance due to the depression of microgalvanic couples. Moreover, the enhanced protective effectiveness of corrosion products was another reason for the improved corrosion resistance.     

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 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.     

Microstructural characteristics and corrosion property of non‐chromate surface treatments on AZ91D magnesium alloy

Chromate conversion coatings can be successfully used for corrosion protection of magnesium alloys. However, the environmental laws have imposed severe restrictions on chromate use in many countries. In this study, a novel protective environmental‐functionally gradient coating was formed on AZ91D magnesium alloy by non‐chromate surface treatments, which consisted of pre‐etching followed by cerium‐based chemical conversion before applying the sol–gel CeO₂ film. It was determined by the analysis of X‐ray diffraction that the gradient coating was mainly composed of CeO₂. The calculation, based on the Scherrer formula, further revealed the formation of nanocrystalline structure in the coating. Scanning electron microscopy (SEM) observations showed that the coating was homogeneous and compact, no obvious cracked structure occurred. According to the immersion tests, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this novel environmental‐functionally gradient coating.     

Corrosion behaviour of Mg/Al alloys in high humidity atmospheres

The influence of relative humidity (80–90–98% RH) and temperature (25 and 50 °C) on the corrosion behaviour of AZ31, AZ80 and AZ91D magnesium alloys was evaluated using gravimetric measurements. The results were compared with the data obtained for the same alloys immersed in Madrid tap water. The corrosion rates of AZ alloys increased with the RH and temperature and were influenced by the aluminium content and alloy microstructure for RH values above 90%. The initiation of corrosion was localised around the Al–Mn inclusions in the AZ31 alloy and at the centre of the α‐Mg phase in the AZ80 and AZ91D alloys. The β‐Mg₁₇Al₁₂ phase acted as a barrier against corrosion.     

Inhibition of corrosion of AZ91 magnesium alloy in ethylene glycol solution in presence of chloride anions

The influence of chloride ions on the corrosion of AZ91 magnesium alloy in water/ethylene glycol solutions and the inhibiting effect of lactobiono‐tallowamide (LTA) were investigated using electrochemical and surface analysis methods. Potentiodynamic polarization curves in aqueous solution of ethylene glycol (50:50w%) containing 0.1 g.L⁻¹ chloride and up to 0.5 g.L⁻¹ LBT were obtained at room and at elevated temperatures. The chloride anions showed a distinct deteriorating effect as they caused pit initiation and accelerated the dissolution of the tested alloy. The selected organic compound demonstrated good protective properties against corrosion of AZ91 magnesium alloy and behaved as inhibitor of mixed type hindering both the cathodic and the anodic partial reactions. It showed inhibition efficiency of 77% at relatively low concentration of 0.2 g.L⁻¹ and was considered as a promising corrosion inhibitor. The mechanism of inhibition was discussed on the basis of the electrochemical impedance spectroscopy (EIS) and XRD analysis of the surface.     

Thixomolded AZ91D and MRI153M magnesium alloys and their enhanced corrosion resistance

AZ91D and MRI153M alloys were produced by thixomolding. Their corrosion resistance is significantly higher than that of similar materials produced by ingot or die-casting. A corrosion rate smaller than 0.2 mm/year in 5 wt% NaCl solution is measured for the thixomolded AZ91D alloy. The corrosion behaviour was evaluated using immersion tests, electrochemical impedance spectroscopy, hydrogen evolution, glow discharge optical emission spectroscopy, and atomic emission spectroelectrochemistry. A bimodal microstructure is observed for both alloys, with the presence of coarse primary α-Mg grains, fine secondary α-Mg grains, β-phase, and other phases with a minor volume fraction. The amount of coarse primary α-Mg is significantly higher for the AZ91D compared with the MRI153M. The network of β-phase around the fine secondary α-Mg grains is better established in the thixomolded AZ91D alloy. A combination of several factors such as the ratio of primary to secondary α-Mg grains, localised corrosion or barrier effect due to other phases, as well as regions of preferential dissolution of the α-Mg due to chemical segregation, are thought to be responsible for the high corrosion resistance exhibited by the thixomolded AZ91D and MRI153M.     

Influences of Ca and Y Addition on the Microstructure and Corrosion Resistance of Vacuum Die-Cast AZ91 Alloy

The influences of Ca and Y additions on the microstructure and corrosion resistance of vacuum die-cast AZ91 alloys were investigated by optical microscope,electron scanning microscope,weight-loss test,and electrochemical corrosion experiment.The results indicate that the Ca or Ca and Y additions refined the microstructure and decreased the amount of Mg17Al12 phase on grain boundaries in the alloys.Meanwhile,the addition of Ca and Y led to the formation of network Al2 Ca phase and rod-like Al2 Y phase,improved the corrosion resistance of AZ91 magnesium alloy.Compared with AZ91 alloy,the corrosion rate of AZ91–1.5Ca–1.0Y alloy was decreased to 16.2%,and its corrosion current density was dropped by one order of magnitude after immersion in 3.5 wt% NaCl solution for 24 h.     

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。     

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.     

Cerium-Based Sealing Treatment of Mg–Al Hydrotalcite Film on AZ91D Magnesium Alloy

An environment-friendly cerium-based sealing treatment was developed to improve the surface integrity and corrosion resistance of Mg–Al hydrotalcite film on AZ91D magnesium alloy. The cerium dioxide was generated through three stages namely nucleation, growth and dissolution, modifying the surface of AZ91D Mg alloy, and the hydrotalcite film became integral after being treated for 30 min. The results of polarization curves showed that the anti-corrosive performance of the hydrotalcite film was enhanced by the sealing treatment. Moreover, the immersion tests and electrochemical impedance spectrum measurements also demonstrated that the sealed hydrotalcite film provided a longer-term protection of magnesium alloy from corrosion as compared to the unsealed one.     

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。     

A novel dual nickel coating on AZ91D magnesium alloy

Magnesium alloys covered with metal coating display excellent corrosion resistance,wear resistance,conductivity and electromagnetic shielding properties.The electroless plating Ni-P as bottom layer following the electroplating nickel as surface layer on AZ91D magnesium alloy was investigated.The coating surface morphology was observed with SEM and the structure was analyzed with XRD.Electrochemical tests and salt spray tests were carried out to study the corrosion resistance.The experimental results indi...     

Corrosion behaviour of Mg–Al alloys with Al–11Si thermal spray coatings

The corrosion resistance of AZ31, AZ80 and AZ91D Mg–Al alloys with Al–11Si thermal spray coatings was evaluated by electrochemical and gravimetric measurements in 3.5 wt% NaCl solution. The changes in the morphology and corrosion behaviour of the Al–11Si coatings induced by a cold‐pressing post‐treatment under 32 MPa were also examined. The as‐sprayed Al–11Si coatings revealed high degree of porosity and poor corrosion protection, which resulted in galvanic acceleration of the corrosion of the magnesium substrates. The application of a cold‐pressing post‐treatment produced more compact Al–11Si coatings with better bonding at the substrate/coating interface and slightly higher corrosion resistance. However, interconnected pores remained in the cold‐pressed coatings due to the low plasticity of the Al–11Si powder and galvanic corrosion of the substrate was observed after immersion in 3.5 wt% NaCl for 10 days.     

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。     

Protection behaviour of surface films formed on AZ91D magnesium alloy in nitrogen/1,1,1,2-tetrafluoroethane atmospheres

Protective surface coatings on an AZ91D magnesium alloy were formed in an atmosphere mixture of nitrogen and 1,1,1,2-tetrafluoroethane (HFC-134a). The surface composition and microstructure were characterized using X-ray diffraction analysis and scanning electron microscopy, respectively. The cross-section morphologies of the coatings show that an increase in conversion time results in an increase in the continuity and compactness of the coating generated on the surface of the AZ91D alloy. The corrosion resistance tests performed by immersion into 3.5% NaCl solutions were investigated by electrochemical measurements. The results showed that the coated samples had higher corrosion resistance than the uncoated alloy. On the other hand, the corrosion density of the coated samples decreased by increasing the conversion time by about two orders of magnitude, compared with the un-coated samples. This behaviour is attributed to the formation of a protective surface film constituted mainly for MgF2, together with other phases. The nature of these phases depends on the process conditions.     

表面纳米化对AZ91D镁合金渗铝行为的影响

镁合金表面渗铝是提高耐蚀性的一种有效方法。本研究将表面纳米化作为渗铝的预处理过程。采用高能喷丸对AZ91D镁合金进行表面纳米化处理,然后进行真空铝扩散得到渗铝层。用透射电镜(TEM)和扫描电镜(SEM)观察了渗铝层的形貌。结果表明,在对AZ91D镁合金表面高能喷丸后获得了100 nm的晶粒尺寸。在高能喷丸之后,渗铝层的深度比未高能喷丸的渗铝层厚。在440℃下扩散12 h后,渗铝层的深度增加到70μm。采用电化学方法对AZ91D镁合金的耐腐蚀性能进行了表征。结果表明,渗铝层明显降低了AZ91D镁合金的腐蚀速率。因此,高能喷丸强化有利于镁合金表面渗铝,提高镁合金的耐蚀性。