Corrosion behavior of PEO-treated AZ31 Mg alloy in chloride solution

Corrosion behavior and resistance of plasma electrolyte oxidation (PEO)-treated AZ31 Mg alloy were investigated by immersion and potentiodynamic polarization tests in 0.5 M NaCl solution in view of the PEO film thickness and sealing treatment of the PEO films in boiling water. The PEO films were formed using pulse current for various durations in 1 M NaOH?+?0.5 M NaF solution. Filiform corrosion was observed during the immersion test while pitting corrosion occurred during the potentiodynamic polarization test, irrespective of sealing treatment of the PEO films. Corrosion resistance of AZ31 Mg alloy was improved remarkably by the formation of thicker PEO films and their sealing treatments.     

Corrosion inhibition of magnesium alloy AZ31 in chloride-containing solutions by aqueous permanganate

In this work, corrosion of the AZ31 magnesium alloy was examined in 0.05 M NaCl solutions containing 0.01–0.150 mol/dm³ of potassium permanganate as a corrosion inhibitor. A set of electrochemical impedance spectroscopy, linear sweep voltammetry, and hydrogen evolution measurements revealed high inhibitor effectiveness at relatively high (0.150 mol/dm³) KMnO₄ concentrations. Based on data of energy-dispersive X-ray analysis, scanning electron microscopy, and Raman spectroscopy, a mechanism of the corrosion inhibition of AZ31 alloy by potassium permanganate in chloride-containing media was proposed.

     

One-step synthesis of lamellar molybdate pillared hydrotalcite and its application for AZ31 Mg alloy protection

A novel anticorrosion pigment for AZ31 Mg alloy protection, molybdate pillared hydrotalcite (HT-MoO₄^2?), was successfully fabricated via a simple one-step process. The physicochemical properties of the samples were well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectra, and inductively coupled plasma (ICP) method, respectively. The results indicated that the material showed typical characteristics of molybdate intercalated hydrotalcite. Additionally, it was found that the sample exhibited nano-sized lamellar morphology with the particle size of 35–60 nm. Moreover, the coating on AZ31 Mg alloy containing HT-MoO₄^2? pigment showed obviously higher corrosion protection performance in comparison with the strontium chromate (SC) pigment by Electrochemical impedance spectroscopy (EIS) measurements. The mechanism of corrosion protection was proposed to be that the HT-MoO₄^2? pigment in the coating would cause the pigment to undergo amphoteric ion exchange with aggressive NaCl solution, leading to the release of molybdate and Zn²⁺ inhibitors.     

阳极氧化AZ91D镁合金在氯化钠稀溶液中的腐蚀行为

利用盐雾实验、极化曲线扫描、电化学阻抗谱和电化学噪声技术等电化学研究方法结合扫描电镜表面观测技术对AZ91D镁合金氧化膜在1%(w)氯化钠溶液中的耐蚀性能进行了评价. 结果表明, 氧化前后的镁合金腐蚀行为发生明显改变, 如未封孔的阳极氧化膜耐中性5%氯化钠盐雾试验时间超过200 h; 氧化后的镁合金自腐蚀电位明显正移, 点蚀诱导期延长; 阳极氧化膜的高频阻抗约为裸露镁合金的数千倍, 这些变化证明阳极氧化处理使镁合金获取了十分优异的耐蚀性能. 首次利用分形维数Df的变化规律初步描述氧化后AZ91D镁合金的腐蚀过程. 可以发现随着浸泡时间的延长, Df呈现出初期快速增长, 随后出现波动, 最后稍有降低的变化过程. 这种现象对应于氧化后AZ91D 镁合金在1%氯化钠溶液中腐蚀的三个阶段.     

AZ31镁合金表面聚吡咯的化学氧化合成及其耐蚀性能

以对甲苯磺酸钠为掺杂剂, 三氯化铁为氧化剂, 用化学氧化聚合法在AZ31 镁合金表面制备聚吡咯(PPy)膜. 采用傅里叶变换红外(FTIR)光谱分析了镁合金表面聚吡咯膜结构, 通过电化学极化曲线、电化学阻抗谱(EIS)研究了其耐蚀性能, 通过扫描电子显微镜(SEM)、X射线能量散射谱(EDS)分析了表面形貌和成分. 和镁合金裸样相比, 聚吡咯膜对镁合金腐蚀有一定的抑制作用. 硅烷预处理改善了镁合金/聚吡咯体系的耐腐蚀性能, 使腐蚀电位较镁合金裸样正移了110 mV, 电流密度减小了约2个数量级.     

Conversion coatings of Mg-alloy AZ91D using trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl)amide ionic liquid

This work reveals the performance of a trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P6,6,6,14][NTf2]) ionic liquid (IL) conversion coating upon AZ91D. Such conversion coatings represent a novel avenue for chromate replacement. An optimization of coating performance was pursued by careful alloy pretreatment to generate a surface on which the coating performs best, as the AZ91 substrate is distinctly different from pure or dilute Mg alloys. The results reveal that a functional conversion coating can be achieved, retarding anodic dissolution kinetics, causing a significant decrease in corrosion rate. The coating efficacy is closely tied to the pretreatment performed, which dictates both the microstructural and electrochemical heterogeneity of the surface. The resulting coatings were found to contain MgxFx and phosphonium cation related components, the proportions of which were dependent on the pretreatment.     

A HREM and Analytical STEM Study of Precipitates in an AZ91 Magnesium Alloy

 The paper focuses on the microstructural characterisation of secondary phases in an AZ91 magnesium alloy. The orientation relationship and atomic structure of semi-coherent Mg/Mg₁₇Al₁₂ interfaces are studied by means of selected area diffraction, EDS and high resolution TEM. Besides the common Mg₁₇Al₁₂ semi-coherent platelets of high density and coarser incoherent Mg₁₇Al₁₂ particles, other, less frequent precipitates were found, rich in Al and Mn. The quasicrystalline nature of these precipitates was detected by means of electron diffraction.     

Electrochemical performance of Mg–9Al–1Zn alloy in aqueous medium

A systematic study on the corrosion and passivation behavior of AZ91D alloy in relation to the influence of concentration, temperature, pH, and immersion time was made in aqueous sulfate solution using electrochemical techniques including open-circuit potential, potentiodynamic polarization and impedance spectroscopy. It was found that the corrosion and pitting potentials (E _corr and E _pit) of the alloy drift to more active values with increasing either concentration (0.01–1.0 M) or temperature (278–338 K) of the test solution, suggesting that sulfate solution enhances the alloy dissolution, particularly at higher temperatures. On the other hand, values of the total film resistance (R _T) indicate that neutral solution (pH 7.0) supports the formation of a better protective layer on AZ91D surface than alkaline (pH 12.5) or acidic (pH 1.0) medium. The growth of a protective film on the alloy surface at short immersion times (up to ∼50 h) is evinced by a rapid positive evolution of E _corr and fast decrease in the corrosion rate (i _corr). However, for a long-term exposure (up to 500 h) E _corr drifts negatively and i _corr increases due to breakdown of the protective film, which causes a decrease in the alloy stability. Fitting the impedance data to equivalent circuit models suitable to each behavior assisted to explore the mechanism for the attack of the sample surface at various testing times. The results obtained from the three studied electrochemical techniques are in good agreement.     

Electrochemical behavior of polypyrrole-coated AZ31 alloy modified by fluoride anions

The electrochemical polymerization of polypyrrole (Ppy) films on AZ31Mg alloys was carried out using cyclic voltammetery in 0.5 M sodium salicylate solution containing 0.25 M pyrrole and different concentration of sodium fluoride (NaF). Corrosion performance of the Ppy film was assessed by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5 % NaCl solution. It was observed that Ppy coatings doped in the presence of 100 ppm NaF provide the best corrosion protection for magnesium and the corrosion potential shifted about 290 mV toward nobler potentials and decrease the corrosion current density about one order of magnitude. The surface analysis of the coatings showed that the addition of F^? dopant anions led to an improvement in the smoothness, thickness, and adhesion quality of the synthesized Ppy coating on the Mg surface. The scanning electron microscopy (SEM) studies of the fluoride-doped Ppy films revealed that the synthesized coating has a closely packed globular structure which was composed of nanoparticles of Ppy.     

十二烷基苯磺酸钠在AZ31镁合金表面的吸附及其缓蚀作用

采用电化学阻抗谱(EIS)和极化曲线研究十二烷基苯磺酸钠(SDBS)对AZ31镁合金在3.5%(w, 质量分数)NaCl腐蚀介质中的吸附行为及缓蚀作用. 结果表明: SDBS可有效抑制AZ31镁合金在NaCl介质中的腐蚀, 其浓度为0.008 mol·L-1时缓蚀效率可达90%以上; 升高温度并不利于提高SDBS的缓蚀效率. SDBS在AZ31镁合金表面主要发生物理吸附, 吸附过程为放热、熵增的自发过程, 近似符合Langmuir单分子层吸附模型; SDBS为混合抑制型缓蚀剂, 但主要抑制阳极反应.     

覆有微弧氧化涂层的AZ91D镁合金在氯化钠溶液中的极化行为

由于结构和成分的影响,覆有微弧氧化涂层的AZ91D镁合金的极化曲线有多种不同的表现形式.事实上,覆有微弧氧化涂层的AZ91D镁合金在NaCl溶液中的极化曲线行为不仅与涂层的主要组成和微观结构有关,也与极化曲线测试条件,如氯离子浓度、溶液pH值、阴极极化程度和样品的暴露面积有关,由于微弧氧化涂层的不稳定性,这些因素通过改变氧化涂层的组成和微观结构,继而影响极化曲线的形状.本文用傅里叶变换显微红外成像和对应的光学照片研究了氧化涂层的成分和结构的变化.结合物理表征,我们提出一个模型,用以阐明微弧氧化涂层组成和结构在NaCl溶液中的变化.对于浸泡在NaCl溶液中的AZ91D微弧氧化涂层,阳极溶解和阴极还原反应的速控步骤分别是传质过程和电荷转移过程.所以从极化曲线上拟合出来的腐蚀电流密度不能准确反映腐蚀速率,而且误差也难以避免.     

XPS study of the effect of aluminium on the atmospheric corrosion of the AZ31 magnesium alloy

The surface characteristics and corrosion behaviour of the AZ31 magnesium alloy exposed to a high relative humidity (RH) atmosphere were investigated. During the first 15 days of humidity test at 98% RH and 50 °C, a significant increase of magnesium carbonate and a decrease of magnesium oxide were detected on the surface film by XPS; after this stage, increased exposure times did not produce substantial changes on the relative amounts of these compounds. The surface film of commercially pure magnesium, also examined for comparison purposes, revealed more magnesium carbonate and less magnesium oxide compared with the AZ31 alloy. Unlike the AZ31 alloy, the surface of pure Mg disclosed almost complete substitution of MgO by magnesium carbonate after 30 days of exposure time. Mass gain values of tested specimens and scanning electron microscope characterisation of corroded surfaces indicated lower corrosion susceptibility of the AZ31 alloy compared with the commercially pure Mg, suggesting superior chemical stability of the oxide/hydroxide film formed over the magnesium–aluminium alloy surface. XPS and energy dispersive X‐ray (EDX) analyses did not revealed any substantial enrichment of aluminium in the corrosion products film on the AZ31 alloy after 30 days of testing. Copyright © 2008 John Wiley & Sons, Ltd.     

Corrosion behavior of magnesium and its alloy in NaCl solution

The electrochemical behavior of cast Mg, AZ91, and cast AZ91 in 0.1 M NaCl solution is investigated by measuring open-circuit potential (OCP), steady-state current-potential, and electrochemical impedance spectra (EIS). The similar electrochemical impedance behavior is found of three corrosion electrodes. There are two capacitances in high-and medium-frequency domains and one inductive loop or component in low-frequency domain. From equivalent circuit simulation, cast AZ91 has the worst corrosion resistance. The EIS results are in good agreement with those obtained by OCP and polarization curves. Based on the Cao theory, a simple corrosion mechanism is put forward, supplying a possible explanation for low-frequency inductive behavior for Mg and its alloy in NaCl solution at OCP. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 878–885. The text was submitted by the authors in English.     

(NaPO3)6对AZ91D镁合金微弧氧化陶瓷层电化学腐蚀特性的影响

在Na2SiO3-KOH电解液体系中添加一定量的(NaPO3)6, 利用微弧氧化(MAO)技术在AZ91D 镁合金表面制备了原位生长的陶瓷层. 采用动电位极化和电化学阻抗谱(EIS)技术研究了添加(NaPO3)6前后, 制备的陶瓷层在3.5%(w) NaCl溶液中的室温电化学行为. 结果表明, 添加(NaPO3)6后, 陶瓷层的自腐蚀电位显著上升, 自腐蚀电流密度明显减小. 这主要是由于(NaPO3)6增加了反应过程中基体镁合金表面的“氧空位”和溶液中PO3-4的含量, 促使元素Mg在金属/膜层(M/F)界面上快速形成相应氧化物, 从而增加了陶瓷层的厚度和致密性. 根据电化学反应体系和陶瓷层的特殊结构, 建立了合理的等效电路, 并结合EIS 数据, 分析了添加(NaPO3)6提高陶瓷层耐电化学腐蚀性能的机理.     

镁合金表面原位生长有机膦酸盐薄膜及耐蚀行为

利用超声辅助的浸渍涂布方法,在AZ91D镁合金表面原位生长了氨基二乙酸亚甲基膦酸镁铝薄膜,其中包含具有纳米尺度的变形六边形板状颗粒。塔菲尔极化曲线、电化学阻抗谱测量表明,修饰后的AZ91D镁合金的耐腐蚀行为依赖于浸渍所用的膦酸浓度、pH值、温度及时间等。在3.5%NaCl溶液中,未修饰的AZ91D其腐蚀活化能是18.1 kJ.mol-1,而在1.5 mmol.L-1膦酸溶液中pH值分别是1.7、11.5时浸渍涂布有机膦酸盐薄膜后,AZ91D的腐蚀活化能分别是27.9、37.8 kJ.mol-1。     

Corrosion behavior of AZ91D magnesium alloy in distilled water

The corrosion of AZ91D magnesium alloy has received extensive attention due to the continuous expansion of its application field in recent years. However, the corrosion of AZ91D magnesium alloy in distilled water is relatively few. In this paper, the corrosion behavior of AZ91D magnesium alloy was studied in distilled water by electrochemical tests in combination with weight loss and surface analysis methods. The results indicated that the corrosion rate of AZ91D magnesium alloy increased with the increase of temperature and immersion time. The increase of the corrosion rate of AZ91D magnesium alloy with the increase of immersion time might be attributed to the damage of the structure of corrosion product film by hydrogen evolution, significantly accelerating the anodic process of AZ91D magnesium alloy. It was interesting that, in distilled water, the EIS of AZ91D magnesium alloy excluded an inductive arc in the low frequency region, which indicated that there was no the adsorption and desorption of aggressive ions or the damage and repair of film. The corrosion product film of AZ91D magnesium alloy in distilled water was composed of a compact inner corrosion product film and a loose outer corrosion product film.     

Surface characteristics of AZ91D alloy anodized with various conditions

Anodic oxidation of an AZ91D magnesium alloy was carried out in an attempt to increase the corrosion resistance. The alloy was placed in an electrolyte containing 0.1 M sodium silicate (Na₂SiO₃), 2.0 M sodium hydroxide (NaOH) and 0.1 M sodium phosphate (Na₃PO₄), and treated with a current density of 100–400 mA/cm² for 1 to 4 min. After the anodic oxidation treatment, the surface characteristics were analyzed by SEM, X‐ray diffraction (XRD) and a surface roughness tester. The corrosion resistance was determined by measuring the corrosion potential and corrosion current density using potentiodynamic polarization in a 3.5 wt% NaCl electrolyte solution. Although the anodic oxidation treatment with the base electrolyte resulted in an arrival voltage ranging from 60 to 70 V, the addition of silicate tended to reduce this arrival voltage by approximately 10–20 V and decrease the critical voltage required for the formation of a porous oxide film. The pore size and film thickness increased with increasing applied current and treatment time. The addition of silicate to the electrolyte resulted in films with a homogeneous pore size and a film thickness increasing with the increasing applied current and treatment time. XRD showed the formation of a new MgO and Mg₂SiO₄ phase. The formation of Mg₂SiO₄ was attributed to the presence of SiO₄^4? in the film. After the addition of silicate, the corrosion potential increased and corrosion current decreased, resulting in improved corrosion resistance. Copyright © 2008 John Wiley & Sons, Ltd.     

pH值对AZ31镁合金表面植酸转化膜在模拟体液耐腐蚀性能的影响

采用沉积的方法在镁合金AZ31表面制备植酸转化膜并研究了pH值的影响. 利用极化曲线和电化学阻抗谱方法测定其耐腐蚀性能,用扫描电子显微镜观察转化膜的表面微观结构,用能谱测定转化膜的组成元素. 在理论上通过热力学的方法分析最佳pH值. 植酸转化膜可以提高镁合金AZ31的耐腐蚀性能. 当植酸溶液的pH=5时腐蚀效率达到了89.19%,此时腐蚀电位正移了156 mV,腐蚀电流密度与没有处理的试样相比减小了约一个数量级. 热力学分析表明植酸转化膜的耐腐蚀性能不仅受植酸根离子和镁离子浓度的影响,也与氢气释放的速率有关.     

Effect of nano-Al2O3 particles and of the Co concentration on the corrosion behavior of electrodeposited Ni–Co alloys

Incorporation of nano-Al₂O₃ particles into a Ni–Co alloy by electrodeposition influences the corrosion properties, morphology, and structure of the layers. The resistance against corrosion of Ni–Co/Al₂O₃ composite films deposited on stainless steel was investigated in a 0.1-M NaCl solution by potentiodynamic polarization. The presence of nanoparticles improves the corrosion resistance of Ni–Co/nano-Al₂O₃ deposits when compared to pure Ni–Co alloy. Moreover, by increasing the pH of the electrodeposition bath and the content of Co in the alloy, the resistance against corrosion is furthermore improved. The morphology of the deposits before and after their corrosion was analyzed by scanning electron microscopy. The presence of the embedded alumina particles in the Ni–Co alloys was one of the key factors that limited further propagation of corrosion on the metallic surface. Preferential corrosion attack, in the form of a pitting corrosion, was located mainly at the grain boundaries.     

AZ91D镁合金上钼改性锌系磷化膜的制备、 结构及性能

采用在磷化液中添加钼酸钠及腐蚀抑制剂的方法, 在AZ91D 镁合金表面上制备了均匀细致的锌系复合磷化膜. 用XRD对膜层的化学组成及结构进行了表征,用SEM和EDS对膜层的形貌和组分含量进行分析. 结果表明, 磷化膜主要由Zn3(PO4)2·4H2O和单质Zn组成. 在磷化液中加入钼酸钠使磷化膜组织更加细致而且无裂纹. 磷化液中的钼酸钠含量为1.5 g/L时, 磷化膜的结晶最致密, 单质锌的含量最高, 耐蚀性最好. 还提出了一种快速测量镁合金表面膜层耐蚀性的试验方法, 同时对镁合金上的磷化反应的机理进行了探讨.