硅氧烷硫化物与铈盐复合膜对铝合金耐点蚀能力的影响

doi:10.11902/1005.4537.2014.227

中国腐蚀与防护学报

2015, Vol. 35

Issue (6): 525-534 DOI: 10.11902/1005.4537.2014.227

研究报告

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硅氧烷硫化物与铈盐复合膜对铝合金耐点蚀能力的影响

郝敬丽¹,高永晶¹,董泽华^1,²(

)

1. 华中科技大学化学与化工学院材料化学与服役失效湖北省重点实验室武汉 430074
2. 湖北文理学院化工与食品学院襄阳 433500

Effects of Siloxane Sulfide and Cerium Salt Complex Conversion Film on Corrosion Resistance of Aluminum Alloy

Jingli HAO¹,Yongjing GAO¹,Zehua DONG^1,²(

)

1. Hubei Key Laboratory of Materials Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
2. School of Chemical and Food Sciences, Hubei Institute of Arts, Xiangyang 433500, China

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摘要:

通过在AA6063铝合金表面预沉积Ce³⁺,再浸涂双-[三- (乙氧基) 硅丙基]四硫化物 (BTST) 的分步沉积工艺,制备了一种高耐蚀性的CeO₂/BTST复合转化膜。结果表明：单独CeO₂膜仅可使铝合金在3%NaCl溶液中的极化电阻提高一个数量级;但复合膜则可使之提高两个数量级,且点蚀电位上升近400 mV。CeO₂/BTST复合膜对铝合金亚稳态或稳态点蚀发展有强烈抑制作用,其噪声电阻达到10 MΩ·cm²以上,在浸泡168 h内基本无亚稳态点蚀发生,而单独的CeO₂膜或BTST自组装膜的耐蚀性均有限,在3%NaCl溶液中浸泡168 h后铝合金表面即出现大量点蚀。由于CeO₂能优先吸附于第二相 (AlFeSi) 组织表面,抑制亚稳态点蚀生长;而硅氧烷与Al—O键结合能高,能有效提高Al基体的全面保护能力,得益于二者的协同作用,采用顺序沉积铈盐/硅氧烷所制备的复合保护层,能同时显著提升铝合金的全面腐蚀与局部腐蚀抗力。

关键词 ：铝合金, 点蚀, 铈盐, 硅氧烷, 转化膜

Abstract：

A complex chemical conversion film of CeO₂-siloxane was prepared on AA6063 aluminum alloy by successively dipping the alloy in CeCl₃ aqueous solution and then in bis-[triethoxysilypropyl] tetra-sulfide (BTST) alcohol solution. Electrochemical tests show that the polarization resistance of the bare Al alloy in 3%NaCl solution can be enhanced by an order of magnitude with the CeO₂ conversion film alone. But the complex film can rise both the polarization resistance by two orders of magnitude and the pitting potential by ca 400 mV. The enhancement of corrosion resistance of the alloy is limited by applying either CeO₂ conversion film or BTST film alone, while a lot of pits can be observed on the Al electrode surface after immersed in 3%NaCl for 300 h. However, after the CeO₂/BTST complex film was formed, no noise peaks can be found from the ECN curves when Al electrode immersed in 3%NaCl for 168 h, indicating that the complex film has a strong inhibition effect on the propagation of metastable- and steady-pits on the aluminium alloy. Since CeO₂ can be absorbed preferentially on the second phase (AlFeSi), it can inhibit the growth of metastable pits; and the siloxane has a high binding energy with Al—O bond, therefore, the synergistic effect of CeO₂ and siloxane may be beneficial to the excellent protectiveness of the complex film.

Key words： aluminium alloy pitting corrosion cerium siloxane conversion film

基金资助:国家自然科学基金项目 (51371087) 资助

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引用本文:

郝敬丽,高永晶,董泽华. 硅氧烷硫化物与铈盐复合膜对铝合金耐点蚀能力的影响[J]. 中国腐蚀与防护学报, 2015, 35(6): 525-534.
Jingli HAO, Yongjing GAO, Zehua DONG. Effects of Siloxane Sulfide and Cerium Salt Complex Conversion Film on Corrosion Resistance of Aluminum Alloy. Journal of Chinese Society for Corrosion and protection, 2015, 35(6): 525-534.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2014.227 或 https://www.jcscp.org/CN/Y2015/V35/I6/525

图1 AA6063铝合金在3%NaCl溶液中浸泡24 h前后的SEM像和浸泡前的EDX结果

图2 不同转化膜下铝合金电极在3%NaCl溶液中浸泡初期的极化曲线和EIS谱

图3 铈盐/硅氧烷顺序浸渍法制备的复合膜及单独的铈盐和硅氧烷膜层下铝合金在3%NaCl 溶液中浸泡不同时间时的电化学噪声(ECN)

图4 不同转化膜下铝合金电极在3%NaCl溶液中的噪声电阻及形核速率随时间的变化曲线

图5 不同转化膜下的铝合金在3%NaCl溶液中浸泡168 h后的腐蚀形貌

图6 不同复合转化膜工艺对铝合金在3%NaCl溶液中的极化曲线和阻抗谱的影响

图7 不同复合转化膜下的铝合金在3%NaCl溶液中浸泡312 h后的腐蚀形貌

图8 铈盐/硅氧烷复合转化膜示意图

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