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.     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

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。     

AZ91D镁合金的微弧氧化陶瓷层电化学腐蚀行为研究

利用微弧氧化技术对AZ91D镁合金在铝酸盐和锫盐溶液中进行表面陶瓷化处理.采用IM6e型电化学工作站,对微弧氧化镁合金进行电化学稳态电流/电位极化曲线测量以及塔费尔斜率测量.通过电化学测量对微弧氧化镁合金的腐蚀行为进行分析.结果表明:镁合金经微弧氧化处理后,点蚀的发生受到限制,镁合金微弧氧化试样的腐蚀电流较原始试样降低4～6个数量级.镁合金微弧氧化试样的耐蚀等级均达到耐蚀以上的等级.     

AZ91D镁合金微弧氧化膜耐蚀性的试验研究

研究了AZ91D镁合金微弧氧化膜在复合铝酸盐溶液中的耐蚀性。利用X射线衍射（XRD）和扫描电子显微镜（SEM）分析了AZ91D镁合金微弧氧化膜的物相和表面形貌；利用IM6e型电化学工作站测量了氧化膜的电化学阻抗和稳态电流／电位极化曲线；利用CMB-1501B型便携式瞬时腐蚀速度测量仪测量了氧化膜的腐蚀电流密度Icorr和年腐蚀深度MMA。试验结果表明，微弧氧化的镁合金耐蚀性提高了2～3个数量级，镁合金微弧氧化膜主要由MgO、MgAl2O4、Al12Mg17组成。     

5083铝合金微弧氧化膜的制备及腐蚀特性

以硅酸盐溶液为电解液,测量了5083铝合金微弧氧化膜的生长曲线.分析了氧化膜的结构、成分和相组成,并通过盐雾腐蚀试验、动电位极化曲线和电化学阻抗谱(EIS)测量,评估了微弧氧化表面处理前后试样的腐蚀特性.微弧氧化初期,电流密度快速下降,膜层主要是向外生长,膜层粗糙度快速增加.氧化30 min后电流密度逐渐降低,膜层逐渐变为向内生长为主.5083铝合金微弧氧化膜由γ-Al2O3和少量莫来石相(3Al2O)3·2SiO2)组成,莫来石主要分布在膜外层中.微弧氧化表面处理的5083铝合金腐蚀电流密度减小2个数量级,电化学阻抗模值|Z|增加,耐腐蚀性能得到了显著的改善.此外,由EIS图谱证实,内层膜致密性对微弧氧化膜耐蚀性起决定作用.     

镁合金表面超声滚压预处理对微弧氧化膜耐蚀性能的影响

镁合金基体首先进行超声滚压预处理后再进行微弧氧化镀膜,结合OM、SEM、EDS、XRD与电化学工作站(模拟体液PBS)对有无超声滚压处理的微弧氧化膜层性能进行测试分析,研究超声滚压处理对镁合金微弧氧化膜层性能的影响。结果表明:超声滚压处理后镁基体表面粗糙度降低、晶粒细化且硬度提升;与镁合金直接微弧氧化的膜层相比,超声滚压预处理之后再进行微弧氧化,膜层中的Si、P、Ca含量比例增大,膜层表面更为致密、光滑,大孔数量明显降低,表面孔隙率由31.7%降低至19.1%;从电化学测试结果看出,与直接微弧氧化的膜层相比超声滚压预处理后膜层的自腐蚀电位高出107 mV,腐蚀电流密度低了一个数量级,并且阻抗性能更优,镁合金超声滚压预处理可有效提升微弧氧化膜层在PBS溶液中的耐蚀性。     

镁合金微弧氧化陶瓷层耐蚀性的电化学分析

采用IM6e型电化学工作站，测试了镁合金微弧氧化后陶瓷层的电化学阻抗(EIS)、稳态电流／电位极化曲(Steady State1／E Recording)以及Tafel斜率。结合测量结果对微弧氧化处理镁合金的耐蚀性进行分析。结果表明，经过微弧氧化处理后试样的电化学阻抗比未经处理原始试样的电化学阻抗高3个数量级。微弧氧化处理过程中存在一个最佳陶瓷层厚度，当超过或低于这个最佳厚度时，试样的耐蚀性都较差，只有达到这个最佳厚度时，试样的耐蚀性才是最佳的。     

(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.     

AM60压铸镁合金表面ZrO_2微弧氧化陶瓷层的制备方法研究

为了改善镁合金的微弧氧化膜层的性能,利用两步法在AM60压铸镁合金表面制备了ZrO_2微弧氧化膜层.研究了膜层在恒电压控制方式下的生长规律,测量了膜层在w(NaCl)=3.5%溶液中的极化曲线,分析了膜层的物相组成.结果表明:在400 V恒压微弧氧化处理时,微弧氧化膜层的平均生长速度最高可达3.5 μm/min:试样在w(NaCl)=3.5%溶液中的极化曲线显示,镁合金经过两步法在锆盐溶液中微弧氧化后,其腐蚀电位正移,腐蚀电流降低,腐蚀速度大幅降低,其耐蚀性得到了大幅度提高.两步法制备微弧氧化膜层主要由ZrO_2、ZrP_2、Mg_3(PO_4)_2、MgF_2相组成,在溶液中添加的Zr元素可以通过微弧氧化处理时的复杂反应进入膜层中,膜层表现出的优异耐蚀性主要源于膜层中存在ZrO_2陶瓷.     

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.     

AZ91D镁合金微弧氧化工艺参数的优化

利用自制微弧氧化装置在硅酸盐体系中对AZ91D镁合金进行微弧氧化处理.采用4因素3水平正交试验,从考察膜层厚度、表面粗糙度和耐蚀性出发,确定了AZ91D镁合金在硅酸盐体系中的最佳工艺参数.结果表明：在最佳工艺条件下,微弧氧化膜呈多孔结构、孔径较小,裂纹较少,分布均匀,膜层较为致密;微弧氧化膜由MgO、Mg2SiO4、MgAl2O4和少量的SiO2组成;室温下,在质量分数为3.5%的NaCl中性溶液中浸泡168 h后,膜层表面未出现明显的点蚀现象,耐蚀性较镁合金基体有了很大提高.     

Corrosion resistance and molecular dynamics behavior of the MAO/SAM composite coatings on magnesium alloy

To improve corrosion resistance of magnesium alloy AZ91D, y-Mercaptopropyltrimethoxysilane (MPTS) was assembled on the surface of micro-arc oxidation (MAO) treated magnesium alloy by self-assembly membrane (SAM) technique. The surface morphology and chemical components of the MAO/SAM composite coatings were analyzed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The corrosion resistance of samples was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy and total immersion tests in a 3.5 wt % NaCl solution. The measured EIS data were simulated by an equivalent circuit. Also the molecular dynamic simulation was used to study the adsorption behavior at the molecular level. The results showed that the surface of magnesium alloy was well covered by the MAO/SAM composite coatings with a better corrosion resistance. Chemical adsorption was formed between the organic molecules and the surface of the MAO coating. The approach presented here afforded an effective alternative for surface modification of magnesium-based materials to meet the many aspects of the application requirements.     

聚苯胺/环氧涂层对AZ91D镁合金耐蚀性能的影响

通过化学氧化法合成本征态及氢氟酸掺杂态聚苯胺(PANI),用红外光谱对其结构进行表征。以环氧树脂为成膜物质,在AZ91D镁合金基体上制备了本征态及氢氟酸掺杂的 PANI/环氧涂层,用EIS方法研究涂层在3.5%NaCl溶液中的耐蚀性,并用SEM对浸泡后基体表面形貌进行观察。实验结果表明,与环氧清漆相比,本征态PANI的加入明显改善了环氧涂层的耐蚀性,而氢氟酸掺杂后进一步提高了PANI/环氧涂层的性能。用XPS对基体表面分析,发现添加聚苯胺的涂层在镁合金表面形成了具有保护作用的产物膜。     

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.     

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.     

SiCw/AZ91镁基复合材料的微弧氧化行为及涂层的耐腐蚀性能

采用微弧氧化表面处理技术在SiCw/AZ91镁基复合材料表面制备保护性涂层.通过与AZ91镁合金对比,研究镁基复合材料的微弧氧化行为及其形貌特征,并采用电化学方法评价了微弧氧化涂层的耐腐蚀性能.结果表明,SiC晶须的存在影响了基底材料表面阻挡层的形成,使复合材料的微弧氧化行为不同于基体合金.与合金相比,在恒电流模式下进行微弧氧化的过程中复合材料的电压随时间的演变趋势不够理想,而且在相同工艺条件下复合材料的起弧时间比合金要长.复合材料在微弧氧化过程中偶尔会出现烧蚀现象.虽然SiC晶须会影响复合材料表面涂层的形成,微弧氧化处理仍然能够增强镁基复合材料的耐腐蚀性能,使其自腐蚀电位提高,腐蚀电流降低.当采用恒压模式制备涂层时,涂层耐腐蚀性能随电压的提高而增强.     

Preparation and characterization of inorganic and organic coatings on AZ91D magnesium alloy with electroless plating pretreatment

In this paper, a protective coating scheme was applied for the corrosion protection of AZ91D magnesium alloy. Electroless Ni coating (EN coating) as bottom layer, electrodeposited Ni coating (ENN coating), and silane‐based coating (ENS coating) as top layer, respectively, were successfully prepared on AZ91D magnesium alloy by combination techniques. Scanning electron microscopy and X‐ray diffraction were employed to investigate the surface and phase structure of coatings, respectively. The electrochemical corrosion behaviors of coatings in neutral 3.5 wt% NaCl solution were evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The corrosion testing showed that the three kinds of coatings all could provide corrosion protection for AZ91D magnesium alloy to a certain extent, and the corrosion resistance of ENN and ENS was superior to EN. In order to further study the corrosion protection properties of ENN and ENS, a comparative investigation on the evolution of EIS of ENN and ENS was carried out by dint of immersion test in neutral 3.5 wt% NaCl solution. The results indicated that, compared with ENN, the ENS could provide longer corrosion protection for AZ91D magnesium alloy. It is significant to determine the barrier effect of each coating, which could provide reference for industry applications.