封闭对铝合金微弧氧化膜在酸性溶液中耐蚀性的影响

doi:10.15541/jim20140582

无机材料学报 ›› 2015, Vol. 30 ›› Issue (6): 627-632.DOI: 10.15541/jim20140582 CSTR: 32189.14.10.15541/jim20140582

封闭对铝合金微弧氧化膜在酸性溶液中耐蚀性的影响

叶作彦¹, 刘道新¹, 李重阳¹, 张晓化¹, 张小明², 雷明霞²

(1. 西北工业大学腐蚀与防护研究所, 西安 710072; 2. 中航工业第一飞机设计研究院, 西安 710089)

收稿日期:2014-11-14 修回日期:2014-12-25 出版日期:2015-06-04 网络出版日期:2015-05-22
作者简介:叶作彦(1987–), 男, 博士研究生. E-mail: yebonpu@126.com
基金资助:
国家自然科学基金(51171154);轻合金加工科学与技术国防重点学科实验室开放课题研究基金(gf201401001)

Effect of Sealing Treatments on the Corrosion Behavior of Micro-arc Oxidation Coating on Aluminum Alloy in Acid NaCl Solution

YE Zuo-Yan¹, LIU Dao-Xin¹, LI Chong-Yang¹, ZHANG Xiao-Hua¹, ZANG Xiao-Ming², LEI Ming-Xia²

(1. Corrosion and Protection Research Laboratory, Northwestern Polytechnical University, Xi'an 710072, China; 2. AVIC the First Aircraft Institute, Xi'an 710089, China)

Received:2014-11-14 Revised:2014-12-25 Published:2015-06-04 Online:2015-05-22
About author:YE Zuo-Yan. E-mail: yebonpu@126.com
Supported by:
National Natural Science Foundation of China (51171154);National Defense key Disciplines Laboratory of light Alloy Procossing Science and Technology, Nachang Hangkong University (gf201401001)

摘要/Abstract

摘要：

为了提高7A85铝合金的耐蚀性, 采用单极性正脉冲微弧氧化(MAO)技术在其表面制备了陶瓷膜层, 并采用稀土铈盐、铬酸盐和SiO₂溶胶对MAO膜进行封闭处理。采用扫描电子显微镜(SEM)、X射线衍射仪和电化学工作站研究了封闭处理对膜层表面形貌、结构和在酸性NaCl溶液中腐蚀行为的影响。实验发现, MAO膜在酸性NaCl溶液中不能有效地保护铝合金基体。稀土铈盐和铬酸盐封闭处理通过沉积水合氢氧化物封闭孔隙, 可以提高MAO膜的耐蚀性。但在酸性溶液中, 封孔物质会和H⁺发生反应而溶解, 故经封闭的MAO试样也会发生腐蚀失效。SiO₂溶胶封闭处理后MAO膜表面覆盖一层凝胶, 使膜层成为完整的致密层, 可以保护铝合金基体在酸性NaCl溶液中免受腐蚀。

关键词: 铝合金, 微弧氧化, 封闭处理, 电化学, 耐蚀性, SiO2溶胶

Abstract:

Ceramic coatings were fabricated on 7A85 aluminum alloy by unipolar positive pulsed micro-arc oxidation (MAO) treatment for enhancing corrosion resistance. A bi-layer coating was formed with large pores between the layers. The outer layer contained several micro pores and cracks. Therefore, cerium nitrate, potash bichromate and SiO₂ sol were adopted to seal the MAO coatings. Scanning electron microscope, X-ray diffraction and electrochemistry instrument were used to investigate the effect of sealing treatments on the surface morphology, coating structure and corrosion resistance of MAO coatings. Results show that the MAO coating can not protect aluminum alloy from acid NaCl solution for the existing of defects. The defects can be sealed by precipitations produced by cerium nitrate and potash bichromate sealing treatment, and corrosion resistance of the MAO coating is improved. However, the sealed coatings also fail in the acid NaCl solution for dissolution of the precipitation. After sealing with SiO₂ sol, the MAO coating is covered with a SiO₂ gel layer has become a compact barrier layer to protect aluminum substrate from corrosion in acid NaCl solution.

Key words: aluminum alloy, micro-arc oxidation, seal treatment, electrochemistry, corrosion resistance, SiO2 sol

中图分类号:

TQ174

叶作彦, 刘道新, 李重阳, 张晓化, 张小明, 雷明霞. 封闭对铝合金微弧氧化膜在酸性溶液中耐蚀性的影响[J]. 无机材料学报, 2015, 30(6): 627-632.

YE Zuo-Yan, LIU Dao-Xin, LI Chong-Yang, ZHANG Xiao-Hua, ZANG Xiao-Ming, LEI Ming-Xia. Effect of Sealing Treatments on the Corrosion Behavior of Micro-arc Oxidation Coating on Aluminum Alloy in Acid NaCl Solution[J]. Journal of Inorganic Materials, 2015, 30(6): 627-632.

图/表 9

图1 铝合金表面MAO膜的XRD图谱

Fig. 1 XRD pattern of the MAO coating on the aluminum alloy

图2 MAO膜截面形貌(a)及其截面元素分布(b)

Fig. 2 Section morphology (a) and elements distribution along cross section (b) of MAO coating A-substrate, B-inner layer, C-outer layer

图3 MAO膜封闭前后表面形貌

Fig. 3 Surface morphologies of MAO coating before and after sealing (a) MAO; (b) MAO+Ce; (c) MAO+Cr; (d) MAO+Si

图4 封孔沉淀物的EDS分析结果

Fig. 4 EDS patterns of the precipitations

图5 封闭前后MAO膜在腐蚀溶液中的电化学阻抗谱

Fig. 5 Electrochemical impedance spectroscopy (EIS) spectra of MAO coatings (a) MAO with and without sealing treatments; (b) EIS fitting curves of MAO coating; (c) EIS fitting curves of MAO+Ce and MAO+Cr; (d) EIS fitting curves of MAO+Si

图6 封闭前后MAO膜结构示意图及阻抗谱拟合电路

Fig. 6 Scheme of MAO coating structure and equivalent circuit of EIS (a) MAO, MAO+Ce and MAO+Cr; (b) MAO+Si

表1 封闭前后阻抗谱拟合值

Table 1 Calculated impedance parameters of MAO coatings

	MAO	MAO+Ce	MAO+Cr	MAO+Si
R_out/ (Ω·cm²)	810.9	5.723×10⁴	1.344×10⁵	6.851×10⁵
R_in/ (Ω·cm²)	4236	1.416×10⁴	2.230×10⁵	6.851×10⁵

图7 各表面状态试样浸泡24 h后表面形貌

Fig. 7 Surface morphologies of samples immersed for 24 h (a) MAO; (b) MAO+Ce; (c) MAO+Cr; (d) MAO+Si

图8 MAO和MAO+Si浸泡后截面光学显微镜照片

Fig. 8 Optical microscope images of MAO and MAO+Si cross- sectional topography (a) MAO; (b) MAO+Si

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封闭对铝合金微弧氧化膜在酸性溶液中耐蚀性的影响

Effect of Sealing Treatments on the Corrosion Behavior of Micro-arc Oxidation Coating on Aluminum Alloy in Acid NaCl Solution

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