AZ镁合金在高氯酸镁溶液中的电化学行为

用失重、线性电位扫描、交流阻抗、恒流放电等多种方法研究了AZ镁合金在1.0 mol/L Mg(ClO4)2溶液中的电化学行为,考察了它们作为镁电池负极材料的性能。浸泡与伏安实验结果表明,AZ21的自腐蚀比AZ31和AZ61严重;AZ21和AZ31的电化学活性优于AZ61,表现为阳极极化小,开路电位负。交流阻抗结果表明AZ21、AZ31、AZ61的Rct值逐渐增加。恒电流放电发现,AZ31的放电电位负且稳定;电流效率为82%,高于AZ21和AZ61;滞后时间2 s,小于AZ21和AZ61。可望用于Mg电池。     

Effects of benzotriazole on anodized film formed on AZ31B magnesium alloy in environmental-friendly electrolyte

An environmental-friendly electrolyte of silicate and borate, which contained an addition agent of 1H-benzotriazole (BTA) with low toxicity (LD50 of 965 mg/kg), was used to prepare an anodized film on AZ31B magnesium alloy under the constant current density of 1.5 A/dm² at room temperature. Effects of BTA on the properties of the anodized film were studied by scanning electron microscopy (SEM), energy dispersion spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), loss weight measurement, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), respectively. The results demonstrated that anodized growth process, surface morphology, thickness, phase structure and corrosion resistance of the anodized film were strongly dependant on the BTA concentration, which might be attributed to the formation of an BTA adsorption layer on magnesium substrate surface. When the BTA concentration was 5 g/L in the electrolyte, a compact and thick anodized film could provide excellent corrosion resistance for AZ31B magnesium alloy.     

Characterization of the corrosion performances of as-cast Mg–Al and Mg–Zn magnesium alloys with microarc oxidation coatings

In the present study, corrosion-protective microarc oxidation (MAO) coatings were prepared on AZ31B, AZ80, and ZK60 cast magnesium alloy substrates in an alkaline silicate electrolyte. The corrosion performances of the uncoated and MAO-coated alloys were investigated using electrochemical and salt spray chamber corrosion tests. The microstructure characterization and experimental results show that among the three alloys studied, the ZK60 Mg alloy exhibited the best and AZ31B the least corrosion resistance under the salt spray conditions. The MAO coating provided robust corrosion protection of the Mg substrates and resulted in a significant decrease in the corrosion rate of the alloys by 3–4 orders of magnitude. The MAO coating on ZK60 alloy showed better corrosion protectiveness than that on the AZ series alloys due to the incorporation of different alloying elements in the coating, especially the Zn and Al elements, which are from the Mg substrate. The corrosion performances and mechanisms of the uncoated and MAO-coated Mg alloys are interpreted in terms of the microstructure and phase/chemical compositions of both the substrates and coatings.     

Microstructures and properties of aluminum film and its effect on corrosion resistance of AZ31B substrate

Aluminum films with thickness of 8.78-20.82μm were deposited on the AZ31B magnesium alloys by DC magnetron sputtering.The influences of aluminum film on the micro-mechanical properties and corrosion behavior of the magnesium alloys were investigated.The morphology of aluminum film was examined by scanning electron microscopy and the microstructure of aluminum film was analyzed by X-ray diffiactometry.Nanoindentation and nanoscratch tests were conducted to investigate their micromechanical properties.More...     

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。     

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.     

Influence of inorganic acid pickling on the corrosion resistance of magnesium alloy AZ31 sheet

Surface contaminants as a result of thermo-mechanical processing of magnesium alloys, e.g. sheet rolling, can have a negative effect on the corrosion resistance of magnesium alloys. Especially contaminants such as Fe, Ni and Cu, left on the surface of magnesium alloys result in the formation of micro-galvanic couples and can therefore increase corrosion attack on these alloys. Due to this influence they should be removed to obtain good corrosion resistance.In this study, the effect of inorganic acid pickling on the corrosion behaviour of a commercial AZ31 magnesium alloy sheet was investigated. Sulphuric, nitric and phosphoric acids of different concentrations were used to clean the alloy for various pickling times. The surface morphology, composition and phases were elucidated using scanning electron microscopy, X-ray fluorescence analysis, spark discharge-optical emission spectroscopy, energy dispersive X-ray spectroscopy and infrared spectroscopy. The effect of surface cleaning on the corrosion properties was studied using salt spray test and electrochemical impedance spectroscopy. The experimental results show that acid pickling reduces the surface impurities and therefore enhances the corrosion resistance of the alloy. The cleaning efficiency of the three acids used and the corrosion protection mechanisms were found to be remarkably different. Best corrosion results were obtained with nitric acid, followed closely by phosphoric acid. Only the sulphuric acid failed more or less when cleaning the AZ31 sheet. However, to obtain reasonable corrosion resistance at least 5 μm of the surface of AZ31 magnesium alloy sheet have to be removed.     

The influence of carbon nanotubes on the corrosion behaviour of AZ31B magnesium alloy

Carbon nanotubes (CNTs) are an effective reinforcement for magnesium (Mg) and its alloys due to their excellent mechanical properties. However, due to their quite different electrical properties compared to other carbon allotropes, the influence of CNTs on the corrosion of Mg is expected to be different. For this reason, the corrosion of AZ31B Mg alloy based composite with CNTs (AZ31B/CNT composite) was investigated with immersion tests, polarization tests and surface potential measurements. The galvanic corrosion between the Mg matrix and CNTs played an important role in the corrosion behaviour of the AZ31B/CNT composite.     

AZ31镁合金沉积类金刚石薄膜的表面形貌和腐蚀行为

为了改善镁合金的耐蚀性,扩展其应用范围,采用等离子全方位离子镀膜技术在AZ31镁合金表面沉积了含有Si-N和Si-O的2种类金刚石(Diamond-like carbon,DLC)薄膜,研究了其表面形貌及其在3.5%NaCl溶液中的腐蚀行为,探究了DLC薄膜对AZ31镁合金腐蚀行为的影响。利用SEM和AFM观察了AZ31镁合金表面沉积DLC薄膜的表面形貌,采用电化学法测试表面沉积DLC薄膜的AZ31镁合金在3.5%NaCl溶液中的极化曲线和开路电位,通过拉伸试验测试其在空气和3.5%NaCl溶液中的应力应变。结果表明:镁合金试样表面的DLC薄膜光滑致密,在3.5%NaCl溶液中表面沉积DLC薄膜AZ31镁合金的极化行为与表面未沉积DLC薄膜AZ31镁合金相似,表面沉积DLC薄膜AZ31镁合金电位正向移动,耐蚀性提高;与表面未沉积DLC薄膜AZ31镁合金相比,在空气中,表面沉积DLC薄膜AZ31镁合金极限抗拉强度与其接近,延伸率略低;在3.5%NaCl溶液中,表面沉积DLC薄膜AZ31镁合金极限抗拉强度略有降低,延伸率略高。     

Electrochemical Performance of AZ31 Magnesium Alloy under Different Processing Conditions

为选择一种高性价比的镁电池阳极材料,借助电化学工作站、光学显微镜(OM)、扫描电子显微镜(SEM)和X射线能谱分析(EDS)对不同加工状态的AZ31B镁合金电化学性能进行研究。分别将挤压、轧制、铸轧和铸态AZ31B镁合金作为阳极材料,测试其电化学性能。结果表明,在4种加工状态下,挤压态镁合金是性价比最高的一种阳极材料;其组织由均匀细小的晶粒和第二相组成,拥有最负的平衡电位,最低腐蚀电流密度和最小自腐蚀速率;挤压态样品腐蚀后,表面产生疏松细小,且均匀分布的腐蚀产物,降低了阳极极化,增加了阳极利用率。轧制和铸轧态的AZ31B镁合金的电化学活性和耐蚀性能相对挤压态的较低。铸态AZ31B镁合金由于较粗大的晶粒、第二相和铸造缺陷,表现出不稳定的放电曲线和较正的放电电位。不同状态AZ31镁合金的腐蚀均以点蚀为主。     

Biodegradation and cytotoxic properties of pulse anodized Mg alloys

Magnesium has the potential to be used as an implant material owing to its non-toxicity. On the other hand, magnesium alloys corrode rapidly in subcutaneous gas bubbles. Consequently, the approach of using magnesium alloys as a biodegradable biomaterial is not well established. Therefore, the aim of this study was to provide corrosion protection by anodizing to surface for a biodegradable material. Micro-arc oxidation by pulsed DC was applied to AZ91D and AZ31B, and the cell bioactivity was defined. The anodic film was characterized by XRD and SEM. The specific mass loss variation from immersion test and potentiodynamic electrochemical test was performed for the quantification of corrosion resistance. Although the AZ91D had better corrosion resistance properties but the result of the in vitro tests showed low cell viability compared with the AZ31B. The results of the cell staining and agar overlay test revealed the AZ31B group had good biocompatibility and a low corrosion rate. In this study, the surfaces of AZ91D and AZ31B showed the formation of a uniform film by pulse power anodization improving corrosion resistance. Also, the cytotoxicity of the materials was examined by the aluminum content change of compound metal.     

Corrosion properties ofAZ31 magnesium alloy and protective effects of chemical conversion layers and anodized-coatings

The corrosion properties of AZ31 magnesium alloys were studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy（E1S） techniques, meanwhile, the protective properties of two environmentally protective types of chemical conversion layers and anodized coatings of AZ31 magnesium alloys were also discussed. The component of chemical conversion bath is NaH2PO4·12H2O 20 g/L, H3PO4 7.4 mL/L, NaNO2 3 g/L, Zn（NO3）2·6H2O 5 g/L and NaF 1 g/L, and components of the anodization bath is Na2SiO3 60 g/L, C6H5Na3O7·2H2O 50 g/L, KOH 100 g/L and Na2B4O7·2H2O 20 g/L. The results show that the corrosion resistance of AZ31 magnesium increases with the increase of pH value of the corrosive medium. For the chemical conversion layer acquired at 80 ℃, 10 min is the best processing time and the charge transfer resistance of the chemical conversion layer is enhanced nearly by 10 times. The optimum processing time for the anodization of AZ31 is 60 min, the charge transfer resistance value of the anodized sample at the early immersion stage is nearly 26 times of that of the blank sample and the corrosion type of the anodized samples is pitting.     

Study on microstructure and properties of laser surface melted layer of AZ31B magnesium alloy

An attempt has been made to improve the surface properties of AZ31B magnesium alloy through solid solution hardening and refinement of microstructures using a CO_2 laser as a heat generating source. X-ray diffraction (XRD) was used to identify the phases. Microstructure and properties of laser melted layer of AZ31B magnesium alloy were observed or tested by means of optical microscope (OM), scanning electron microscope (SEM), micro-hardness equipment and electrochemical corrosion equipment etc. The results show that the microstructure of laser melted layer becomes finer significantly and uniform. Compared with the substrate, the content of β-Mg_(17)Al_(12) phase of melted layer decreases comparatively. Microhardness of the laser melted layer is improved to 50-95HV_(0.05) as compared to 40-45HV_(0.05) of the AZ31B Mg alloy substrate. The results of electrochemical corrosion show that the corrosion resistance of laser surface melted layer has been improved.     

十六烷基三甲基溴化铵对镁合金腐蚀行为的影响

采用动电位极化和电化学阻抗等方法检测了十六烷基三甲基溴化铵(CTAB) 对AZ31镁合金在3.5% NaCl溶液中腐蚀行为影响的规律, 用扫描电镜观察表面腐蚀产物膜的形貌并分析其组成. 结果表明, 当NaCl溶液中加入2000~3500 mg/L CTAB时, 镁合金的腐蚀速率降低, 且CTAB浓度为3500 mg/L时, 镁合金的腐蚀速率最低. 这主要是因为CTAB在镁合金表面发生吸附, 使阳极溶解过程受阻, 同时, CTAB减少了腐蚀产物膜内的微观缺陷数量, 减少了腐蚀介质的渗入通道, 增大了电荷转移阻力, 从而使镁合金的耐蚀性得到改善.。     

镁合金表面层层组装PSS/PAH膜诱导钙磷涂层

目的镁合金具有良好的生物相容性和可降解性,作为生物医用材料具有广泛的应用前景。有效地提高镁合金的耐蚀性能,对镁合金作为医用材料具有重要意义。方法利用浸泡法在AZ31镁合金基体表面层层组装制备聚苯乙烯磺酸钠(PSS)、聚丙烯胺盐酸盐(PAH)多层膜,并将获得的样品采用水热法在Ca(NO)_3、NaH_2PO_4、Na_2CO_3溶液中诱导钙磷涂层(羟基磷灰石)的形成。利用高分辨扫描电子显微镜、傅里叶红外光谱、X射线光电子能谱对Ca-P/(PAH/PSS)5/Mg复合膜层的表面形貌、化学成分进行了表征,通过析氢和电化学实验(包括极化曲线及阻抗谱)研究了Ca-P/(PAH/PSS)5/Mg涂层的耐腐蚀性能。结果Ca-P/(PAH/PSS)5/Mg膜层厚度约为7.67μm,表现为立体叶草状,在镁合金表面紧密排列。Ca-P/(PAH/PSS)5/Mg涂层耐蚀性提高一个数量级,其腐蚀电流密度从镁合金AZ31的3.69×10–5 A/cm2降低到1.61×10–6 A/cm~2,同时析氢速率降低。结论该涂层可以有效地提高镁合金的耐蚀性能,其成因则主要归功于组装的两种聚电解质的类生物矿化作用。这种诱导所得钙磷膜层对镁合金在生物医用领域的应用提供了新的思路。     

磷酸钠在NaCl溶液中对AZ31镁合金的缓蚀作用

采用电化学阻抗法、动电位极化曲线法、全浸泡失重法和扫描电镜,研究了在3.5%(质量分数)Na Cl溶液中磷酸钠(Na3PO4)对AZ31镁合金腐蚀的抑制作用。结果表明:Na3PO4对3.5%Na Cl溶液中的AZ31镁合金具有缓蚀作用,其缓蚀率随着Na3PO4含量增大逐渐提高,当Na3PO4质量浓度为1.0 g/L时,缓蚀率达到81.5%。结合扫描电镜分析表明,Na3PO4在镁合金表面形成含有Mg(OH)2和Mg3(PO4)2的保护层,这层致密的膜减少了基体与Cl-接触,抑制了镁合金的阳极反应。     

Anti-corrosion performance of a new silane coating for corrosion protection of AZ31 magnesium alloy in Hank's solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.     

Characterization of anodic films formed on AZ91D magnesium alloy

Anodization of die-casted AZ91D magnesium alloy was performed in 3 M KOH+0.21 M Na₃PO₄+0.6 M KF base electrolyte with and without Al(NO₃)₃ addition. The anodic film was characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the various anodized alloys was then evaluated in 3.5 wt % NaCl solution using electrochemical impedance spectroscopy (EIS) and immersion testing. The results showed that the anodic film was mainly composed of MgO. The addition of Al(NO₃)₃ into the base electrolyte results in the formation of Al₂O₃ and Al(OH)₃ in the anodic film. The maximum amount of Al₂O₃ was found in the anodic film when the alloy was anodized in the electrolyte containing 0.15 M Al(NO₃)₃. The results of EIS analysis and morphological examination showed that the MgO anodic film modified with Al₂O₃ exhibited the superior corrosiom resistance for AZ91D Mg alloy.     

Influence of silane on corrosion resistance of magnesium alloy AZ31 with thermally sprayed aluminum coatings

Aluminum coatings on Mg alloy AZ31 were fabricated using the thermal spraying technique, and then sealed with silane.The surface morphology and chemical groups were discerned using scanning electron microscopy and examined using Fourier transformation infrared spectroscopy, respectively.The salt fog tests and the potentiodynamic electrochemical technique were applied to evaluate the influence of silane on corrosion of the AZ31 alloy with aluminum coatings.The results showed that the corrosion resistance of ...     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.