镁合金黑色微弧氧化膜在NaCl溶液中腐蚀电化学演变

目的 评价镁合金黑色微弧氧化热控膜层在氯离子作用下的腐蚀演变行为.方法 在电解液中添加不同浓度的添加剂制备微弧氧化膜层,分析不同微弧氧化膜试样在0.1 mol/L NaCl溶液中的电化学演变过程.采用电化学极化、电化学交流阻抗表征和拟合,结合扫描电镜等方法,对膜层演变规律及机理进行了探讨.结果 未经微弧氧化的镁合金自腐蚀电流密度为17.7 μA/cm2,自腐蚀电位为-1.464 V;经微弧氧化后,试样自腐蚀电流密度减小至0.09 μA/cm2,自腐蚀电位下降至-1.628 V.添加剂加入后制备的微弧氧化膜相比于镁合金基体,其耐蚀性能提高,且随着添加剂浓度的增加,耐蚀效果呈现先增加、后减弱的趋势,添加剂质量浓度在10 g/L时制备的膜层具有最好的防腐效果.镁合金微弧氧化热控膜层在NaCl溶液中腐蚀过程分为三个阶段:一是腐蚀性离子进入多孔膜层,引起界面熔融层变化;二是MgO与水分子反应造成内层膜更加致密,阻抗有所增加;三是腐蚀溶液接触到部分镁合金基底,发生电化学腐蚀,形成楔形效应,引发裂纹,最终导致局部腐蚀失效.结论 微弧氧化提高了膜层的耐蚀性能,其在0.1 mol/L NaCl溶液中的腐蚀过程可分为介质进入孔内、水合反应和局部腐蚀三个阶段.     

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.     

(Al_2O_3-SiO_2)_(sf)／AZ91D镁基复合材料微弧氧化膜的制备及电化学阻抗谱分析

在硅酸盐电解液体系中,采用交流微弧氧化方法在增强体体积分数为33%的(Al_2O_3-SiO_2)_(sf)/AZ91D镁基复合材料表面制备出完整的保护性氧化膜.利用SEM,EDS和XRD分析了氧化膜的形貌、成分和相组成,测量了膜层的显微硬度分布.采用电化学阻抗谱(EIS)评价了微弧氧化表面处理前后复合材料的电化学腐蚀性能,确立了不同浸泡时间对应的等效电路.结果表明,微弧氧化膜主要由MgO和Mg_2SiO_4相组成,最大硬度达到1017 HV.氧化膜电化学阻抗模值|Z|与镁合金基体相比大幅度提高,耐腐蚀性能明显高于基体.在3.5%NaCl溶液里浸泡96 h后,EIS出现感抗弧,显示膜内部开始出现点蚀破坏.氧化膜耐蚀性由膜内致密层特性所决定.     

AZ91D镁合金复合涂层在NaCl溶液中的腐蚀行为

利用微弧氧化和化学镀镍在AZ91D镁合金表面制备了复合涂层,采用动电位极化曲线测试和电化学阻抗测试等方法研究微弧氧化和化学镀镍复合涂层在3.5%NaCl溶液中的腐蚀行为。结果表明,复合涂层使基体镁合金的腐蚀电位提高了1.339V,自腐蚀电流密度降低为基体的1/10;在浸泡初期和中期,复合涂层通过阻碍腐蚀介质向基体的传质和腐蚀产物的输运提高了镁合金的耐腐蚀性,经270h的浸泡,复合涂层完全失效。     

PREPARATION OF MICROARC OXIDATION COATING ON (Al2O3-SiO2)sf/AZ91D MAGNESIUM MATRIX COMPOSITE AND ITS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPIC ANALYSIS\par

在硅酸盐电解液体系中, 采用交流微弧氧化方法在增强体体积分数为33%的 (Al₂O₃-SiO₂)_sf/AZ91D镁基复合材料表面制备出完整的保护性氧化膜. 利用SEM, EDS和XRD分析了氧化膜的形貌、成分和相组成, 测量了膜层的显微硬度分布. 采用电化学阻抗谱(EIS)评价了微弧氧化表面处理前后复合材料的电化学腐蚀性能, 确立了不同浸泡时间对应的等效电路. 结果表明, 微弧氧化膜主要由MgO和Mg₂SiO₄相组成, 最大硬度达到1017 HV. 氧化膜电化学阻抗模值|Z|与镁合金基体相比大幅度提高, 耐腐蚀性能明显高于基体. 在3.5%NaCl溶液里浸泡96 h后, EIS出现感抗弧, 显示膜内部开始出现点蚀破坏. 氧化膜耐蚀性由膜内致密层特性所决定.     

镁合金微弧氧化膜耐蚀性表征方法的对比研究

制备结构、性能相近的AZ91D镁合金微弧氧化膜,通过浸泡、点滴及电化学实验表征膜层的耐蚀性,并结合SEM分析膜层腐蚀前后的表面形貌。本研究中6种耐蚀性检测方法的结果均表明：AZ91D镁合金经微弧氧化处理后耐蚀性显著提高; 失重与增重现象的共存使浸泡实验不能准确评定微弧氧化膜层耐蚀性的优劣; 点滴实验可以较快较准确地反映膜层的耐蚀性,但采纳点滴液开始变色的时间点为评价依据更合适,且测试耐蚀性较好的膜层时,点滴液中硝酸的含量提高到标准中的至少两倍时,才能达到快速检测的目的; 循环伏安、Tafel 极化、开路电位和电化学阻抗谱4种电化学实验能反映诸如腐蚀电位、腐蚀电流密度、阻抗值等更多的信息,可以进一步研究膜层的耐蚀原因。膜层的耐蚀性除了与膜厚、化学成分有关外,还与微观结构膜层内部和表面的密切相关。     

脉冲频率对镁合金微弧氧化膜层在仿生液中耐蚀性的影响

研究了微弧氧化过程中不同电源脉冲频率下制备的膜层在仿生液中的电化学腐蚀行为。对膜层及腐蚀产物的微观组织,孔隙率,腐蚀形貌及相组成进行了分析。采用动电位极化曲线(Tafel)和电化学阻抗谱(EIS)法对膜层的耐腐蚀性能进行评价。结果表明,脉冲频率对AZ31镁合金微弧氧化膜层的耐蚀性有重要影响,随着频率的增加,腐蚀电流密度减小,而电化学阻抗增大。因此在本研究范围内,频率3000 Hz下制备的微弧氧化膜层具有最强的耐腐蚀性能。     

镁合金表面微弧氧化陶瓷膜的腐蚀失效机理

采用全浸和盐雾试验研究了镁合金两类微弧氧化膜层的耐蚀性,并根据它们在5%NaCl水溶液中浸泡不同时间的开路电位、表面形貌及交流阻抗谱的变化,分析了微弧氧化膜层的腐蚀失效机理.研究表明:磷酸盐系膜层和硅酸盐系膜层均可极大提高AZ91D合金的耐蚀性能,但硅酸盐系膜层的耐蚀性要优于磷酸盐系膜层的耐蚀性;微弧氧化膜层的腐蚀失效主要经历了4个阶段:溶液渗入多孔层的孔隙中;一些孔隙内被腐蚀产物所充满;微孔底部的阻挡层逐渐被腐蚀;阻挡层失效,腐蚀过程趋于稳定.     

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。     

AZ91镁合金表面微弧氧化与化学镀铜复合处理层的微观组织与性能

采用微弧氧化技术在AZ91镁合金表面制备Mg O陶瓷膜层,然后在该膜层通过化学镀铜技术制备金属铜层。利用SEM,XRD,EDS,电化学实验及四探针测试等手段研究了复合膜层的显微结构、相组成、耐蚀性和导电性。结果表明:微弧氧化处理获得以Mg O为主相的陶瓷层可有效提高镁合金的耐蚀性,平均厚度为2.5μm的化学镀铜层连续均匀地覆盖在微弧氧化陶瓷层表面,渗入并填充微弧氧化陶瓷层内部呈网状分布的孔隙,形成交错咬合状态;复合膜层表面的导电性良好,与基体镁合金相比,复合膜层的腐蚀电位提高了0.2 V,腐蚀电流密度下降了一个数量级。但由于化学镀铜层与基体镁合金之间产生的电偶腐蚀,导致复合膜层的耐蚀性较陶瓷层有所下降。     

20% Al2O3-SiO2(sf)/AZ91D镁基复合材料微弧氧化陶瓷层电化学腐蚀性能

在磷酸盐体系电解液中,对20%(体积分数)硅酸铝短纤维(Al2O3-SiO2)增强AZ91D镁基复合材料进行微弧氧化表面处理获得陶瓷层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪分析陶瓷层的表面形貌、截面组织和相组成,采用动电位极化和电化学阻抗谱(EIS)测试评价微弧氧化陶瓷层的电化学腐蚀性能。结果表明,该陶瓷层主要由MgO和MgAl2O4相组成。陶瓷层的腐蚀电流密度比镁基复合材料基体低3个数量级,电化学阻抗大幅升高,耐腐蚀性能明显高于复合材料基体     

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.     

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.     

纯镁表面等离子体电解渗硼与微弧氧化复合膜的制备及耐蚀性

目的 在纯镁表面制备新型复合膜,以提高其耐蚀性.方法 先在硼砂系电解液中对纯镁进行等离子体电解渗硼(PEB)处理,预制表面改性层,然后在硅酸盐系电解液中对其进行微弧氧化(MAO)处理,从而获得PEB+MAO新型复合膜.分别使用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析膜层的微观结构、元素分布及物相组成,膜层的耐蚀性则通过动电位极化曲线和电化学阻抗谱(EIS)来表征.结果 纯镁的等离子体电解渗硼过程经历了电离、置换、吸附和扩散四个阶段,获得的PEB表面改性层由氧化层和扩散层组成.在PEB+MAO复合膜的生长过程中,膜层在其厚度方向存在重叠的现象,而不是逐层的简单堆积.等离子体电解渗透时,硼元素渗入后所形成的渗层区域降低了纯镁基体表面的化学活性,改善了其微观组织结构,进而使PEB+MAO复合膜的腐蚀电流密度较基体、单一PEB改性层和单一微弧氧化膜层分别降低了3、2、1个数量级.同时,EIS研究也表明,PEB+MAO复合膜可以提供相对较长时间的抗蚀保护.另外,分析了PEB表面改性层的生成机理以及PEB+MAO复合膜的形成过程,并建立了物理模型.结论 PEB预处理会显著影响PEB+MAO复合膜的厚度、致密性及成分,继而明显提高纯镁的耐蚀性.该新型的复合膜制备方法有望进一步推广到镁合金上,以提高其耐蚀性和承载能力.     

微弧表面处理对AZ31B镁合金耐腐蚀及耐腐蚀疲劳性能的影响

采用微弧表面处理技术(微弧氧化MAO和微弧复合MCC)在AZ31B镁合金基体上制备出不同断面结构的防护涂层。通过电化学腐蚀及腐蚀疲劳测试方法,研究了MAO、MCC涂层的电化学腐蚀及腐蚀疲劳性能。结果表明,生长10 min的MAO涂层具有较好的耐电化学腐蚀性能。MAO涂层表面存在微孔和微裂纹,在应力条件下微孔和微裂纹作为疲劳断裂的裂纹萌生点,可加速裂纹的萌生与扩展,使其腐蚀疲劳寿命相较AZ31B合金基体降低了55%。而具有MCC涂层的AZ31B合金试样腐蚀疲劳极限为(64.0±5.4) MPa,比AZ31B合金基体提高了59%。在低应力载荷下(＜80 MPa),微弧复合涂层试样的腐蚀疲劳强度得到明显提高。     

Characteristics of anodic coatings oxidized to different voltage on AZ91D Mg alloy by micro‐arc oxidization technique

With increasing applied voltage, three types of anodic coatings, passive film, micro‐spark ceramic coating and spark ceramic coating were made by micro‐arc oxidization (MAO) technique on AZ91D magnesium alloy in alkali‐silicate solution. The structure, composition characteristics and the electrochemical properties of coatings were also studied with SEM, XRD and EIS (electrochemical impedance spectroscopy) technique, respectively. It is found that the electrochemical properties are closely related to the structure and composition characteristics of the anodic coatings. At the same time, the characteristics of the three types of anodic coatings differ significantly, among them, the micro‐spark ceramic coating, prepared in the voltage range of 170~220V exhibits compact, homogeneous structure and highest corrosion‐resistance.     

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg−Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation (MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg−Al layered double hydroxide (LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.     

镁合金支架材料AZ81表面PLGA(PTX)/PLLA/MAO涂层的研究

在AZ81镁合金表面制备了抗腐蚀和药物释放复合涂层,并对其耐蚀性、药物释放性能及生物相容性进行研究。DSC和红外光谱数据表明,紫杉醇均匀分散在PLGA体系中。药物释放数据表明30 d后,药物释放率在80%左右。SEM、电化学阻抗、极化及镁离子释放数据表明,PLLA涂层通过有效填充微弧氧化膜表面的微孔与裂缝提高了镁合金的耐腐蚀性。血液和细胞实验表明涂层镁合金血液相容性良好,无细胞毒性。