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中国腐蚀与防护学报  2016, Vol. 36 Issue (4): 295-305    DOI: 10.11902/1005.4537.2015.142
  研究报告 本期目录 | 过刊浏览 |
无溶剂环氧防腐涂层在模拟海水冲刷条件下的电化学行为
赵洪涛,陆卫中(),李京,郑玉贵
中国科学院金属研究所 沈阳 110016
Electrochemical Behavior of Solvent-free Epoxy Coating during Erosion in Simulated Flowing Sea Water
Hongtao ZHAO,Weizhong LU(),Jing LI,Yugui ZHENG
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
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摘要: 

通过EIS对3种无溶剂环氧防腐涂层在60 ℃下流速为2 m/s、含1%(质量分数) 石英砂的模拟海水环境中的失效行为进行了研究,并利用SEM观察了冲刷后涂层的表面形貌,利用激光共聚焦显微镜 (CLSM) 观察了涂层/金属的断面形貌。结果表明,与静态条件相比,流动含砂条件明显加速了无溶剂涂层的失效过程。冲刷条件下,胺类固化环氧粉末涂层和酚醛胺固化环氧液体涂层由于固化交联速度慢,结构比较致密,失效过程主要分为3个阶段：介质在涂层中传输阶段、基体金属腐蚀发生阶段和基体金属腐蚀发展与涂层失效阶段;酚醛固化环氧粉末涂层由于固化速度快,内部孔隙较多,涂层较快形成贯穿通道,失效中期阶段缩短且不明显,失效过程主要为两个阶段。研究结果表明,涂层体系内部存在孔隙是加速涂层失效的一个重要因素。
关键词 ： 无溶剂环氧防腐涂层,  冲刷,  海水,  电化学行为,  孔隙    
Abstract：

The electrochemical behavior of three solvent-free epoxy coatings on Q345E carbon steel during corrosion-erosion induced by flowing slurry of simulated sea water with 1% (mass fraction) of sand at 60 ℃ was investigated by means of electrochemical impedance spectroscopy (EIS), scanning electron microscope (SEM) and confocal laser scanning microscopy (CLSM), respectively. The results showed that the flowing slurry induced erosion aggravated the deterioration of coatings. The amine-cured epoxy powder coating and phenolic aldehyde amine-cured liquid epoxy coating were cured with slow speed and thus much densified, accordingly, their deterioration process experienced three stages: firstly, the inward migration of corrosive medium; secondly, the corrosion initiation of the substrate metal; thirdly, the corrosion propagation of the substrate metal beneath the coating and finally the failure of coatings. On the contrary, the phenolic aldehyde-cured epoxy powder coating was cured with fast speed and thus much porous, its deterioration process experienced two stages with a shortened second stage. Therefore,the existence of pores in the coating is one of the important factors for inducing failure of coatings during corrosion-erosion.
Key words： solvent-free epoxy coating    erosion    sea water    electrochemical behavior    pore
    
基金资助:中国科学院知识创新工程项目 (KGCX2-YW-219) 资助
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赵洪涛
陆卫中
李京
郑玉贵

引用本文:

赵洪涛,陆卫中,李京,郑玉贵. 无溶剂环氧防腐涂层在模拟海水冲刷条件下的电化学行为[J]. 中国腐蚀与防护学报, 2016, 36(4): 295-305.
Hongtao ZHAO, Weizhong LU, Jing LI, Yugui ZHENG. Electrochemical Behavior of Solvent-free Epoxy Coating during Erosion in Simulated Flowing Sea Water. Journal of Chinese Society for Corrosion and protection, 2016, 36(4): 295-305.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2015.142      或      https://www.jcscp.org/CN/Y2016/V36/I4/295

图1  冲刷实验装置示意图
图2  环氧粉末涂层A在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的Bode图
图3  环氧粉末涂层A在60 ℃下3.5%NaCl溶液中静态浸泡不同时间的Bode图
图4  环氧粉末涂层B在60 ℃下3.5%NaCl溶液中流动冲刷条件下浸泡不同时间的Bode图
图5  环氧粉末涂层B在60 ℃下3.5%NaCl溶液中静态浸泡不同时间的Bode图
图6  无溶剂环氧液体涂层C在60 ℃下3.5%NaCl溶液中流动冲刷条件下浸泡不同时间的Bode图
图7  无溶剂环氧涂层C在60 ℃下3.5%NaCl溶液中静态浸泡不同时间的Bode图
图8  环氧粉末涂层A在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的Nyquist图
图9  环氧粉末涂层B在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的Nyquist图
图10  无溶剂环氧液体涂层C在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的Nyquist图
图11  无溶剂环氧涂层体系等效电路图
Timed RcΩcm2 n1 QcFcm-2 RctΩcm2 n2 QdlFcm-2 RdiffΩcm2 n3 QdiffFcm-2 LHcm2 RLΩcm2
0 1.9×1011 1.00 7.5×10-11 --- --- --- --- --- --- --- ---
1.5 4.8×1010 0.91 2.5×10-10 --- --- --- --- --- --- --- ---
4 1.3×109 0.89 3.4×10-10 --- --- --- --- --- --- --- ---
9 2.6×108 0.89 3.7×10-10 1.8×108 0.79 1.5×10-8 --- --- --- --- ---
12.5 6.5×107 0.89 2.9×10-10 --- --- --- --- --- --- 1.2×109 9.6×108
18.5 3.9×105 1.00 9.1×10-11 3.4×105 1.00 8.5×10-11 4.7×105 0.33 2.1×10-7 --- ---
22 1.3×105 1.00 1.1×10-10 2.1×105 0.37 1.8×10-8 3.8×105 1.00 1.1×10-10 --- ---
26.5 7.9×104 0.20 6.8×10-8 2.1×105 1.00 1.3×10-10 1.3×105 1.00 3.4×10-10 --- ---
表1  环氧粉末涂层A在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的EIS拟合结果
Time / d Rc / Ωcm2 n1 Qc / Fcm-2 Rct / Ωcm2 n2 Qdl / Fcm-2 Rdiff / Ωcm2 n3 Qdiff / Fcm-2 Zw
0 1.2×1012 1.00 1.0×10-10 --- --- --- --- --- --- ---
1.5 5.0×1010 0.96 1.5×10-10 --- --- --- --- --- --- ---
4 4.2×1010 0.94 2.8×10-10 --- --- --- --- --- --- ---
9 8.9×106 0.96 2.1×10-10 8.50×107 0.37 2.6×10-9 --- --- --- 1.1×10-7
12.5 8.0×105 0.94 3.1×10-10 5.20×106 0.38 7.0×10-8 2.9×107 0.66 9.1×10-8 ---
15 1.0×106 0.93 3.1×10-10 6.30×106 0.49 4.1×10-8 4.6×106 1.00 2.0×10-6 ---
18.5 5.4×105 1.00 1.4×10-10 1.60×106 0.46 3.1×10-7 1.0×108 1.00 1.2×10-7 ---
22 1.7×105 0.86 9.2×10-10 2.30×106 0.57 4.1×10-7 7.7×1010 1.00 5.9×10-4 ---
26.5 4.8×105 0.89 5.8×10-10 2.55×106 0.46 4.4×10-7 3.4×106 1.00 2.0×10-7 ---
表2  环氧粉末涂层B在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的EIS拟合结果
Time / d Rc / Ωcm2 n1 Qc / Fcm-2 Rct / Ωcm2 n2 Qdl / Fcm-2 Rdiff / Ωcm2 n3 Qdiff / Fcm-2
0 7.5×1010 1.00 6.7×10-11 --- --- --- --- --- ---
1.5 3.3×1010 0.92 2.1×10-10 --- --- --- --- --- ---
4 7.7×109 0.91 2.4×10-10 --- --- --- --- --- ---
9 3.8×108 0.95 1.7×10-10 3.1×108 1.00 1.8×10-10 --- --- ---
12.5 3.5×107 0.95 1.7×10-10 8.3×106 0.66 1.1×10-9 --- --- ---
15 2.1×106 0.96 1.4×10-10 1.6×107 0.05 3.2×10-8 --- --- ---
18.5 2.9×108 0.95 1.8×10-10 1.0×109 0.26 3.2×10-9 --- --- ---
22 1.6×105 0.92 2.8×10-10 1.6×105 0.45 3.2×10-6 2.1×106 1.00 2.1×10-6
26.5 8.5×104 0.83 9.5×10-10 4.6×105 0.52 3.3×10-6 7.7×1014 1.00 2.1×10-6
表3  无溶剂环氧液体涂层C在60 ℃下3.5%NaCl溶液中冲刷条件下浸泡不同时间的EIS拟合结果
图12  60 ℃时环氧粉末涂层A在不同条件下Qc和|Z |0.01 Hz随时间的变化曲线
图13  60 ℃时环氧粉末涂层B在不同条件下Qc和 |Z |0.01 Hz随时间的变化曲线
图14  60 ℃时无溶剂环氧液体涂层C在不同条件下Qc和|Z |0.01 Hz随时间的变化曲线
图15  环氧粉末涂层A、B和无溶剂环氧涂层C体系的CLSM断面形貌图
图16  环氧粉末涂层B和A以及无溶剂环氧液体涂层C在26.5 d冲刷后表面SEM像
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