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中国腐蚀与防护学报  2025, Vol. 45 Issue (6): 1549-1562     CSTR: 32134.14.1005.4537.2025.046      DOI: 10.11902/1005.4537.2025.046
  研究报告 本期目录 | 过刊浏览 |
单组分氟碳改性环氧涂层对碳钢和铝合金长期防腐性能的对比研究
王得1,2, 张璠3, 王兴奇2, 张贺新1, 赵成志1, 杨延格2()
1 哈尔滨工程大学材料科学与化学工程学院 哈尔滨 150001
2 中国科学院金属研究所 师昌绪先进材料创新中心 沈阳 110016
3 沈阳防锈包装材料有限责任公司 沈阳 110000
Long-term Corrosion Resistance of Carbon Steel and Al-alloy with Single Component Fluorocarbon Modified Epoxy Coating
WANG De1,2, ZHANG Fan3, WANG Xingqi2, ZHANG Hexin1, ZHAO Chengzhi1, YANG Yange2()
1 School of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
2 Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
3 Shenyang Rustprooft Packaging Materials Co. Ltd. , Shenyang 110000, China
引用本文:

王得, 张璠, 王兴奇, 张贺新, 赵成志, 杨延格. 单组分氟碳改性环氧涂层对碳钢和铝合金长期防腐性能的对比研究[J]. 中国腐蚀与防护学报, 2025, 45(6): 1549-1562.
De WANG, Fan ZHANG, Xingqi WANG, Hexin ZHANG, Chengzhi ZHAO, Yange YANG. Long-term Corrosion Resistance of Carbon Steel and Al-alloy with Single Component Fluorocarbon Modified Epoxy Coating[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(6): 1549-1562.

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摘要: 

通过开路电位、电化学阻抗谱、动电位极化曲线等电化学测试，结合附着力测试、水接触角测试及宏/微观形貌表征等手段，详细对比研究了一种新型单组分氟碳改性环氧涂层对10#钢和LY12铝合金两种不同金属基体的长期防腐蚀性能。结果表明，通过在3.5%NaCl溶液中长期浸泡3500 h的测试，改性环氧涂层对LY12铝合金的防腐性能优于10#钢。改性环氧涂层在10#钢基体表面的失效分为4个阶段，而在LY12铝合金基体表面则分为3个阶段，且失效历程有所不同，涂层/金属界面的腐蚀是决定涂层是否快速失效的关键。铝合金上低的涂层附着力、高的水接触角以及碳钢基体上高的涂层附着力、低的水接触角是造成涂层具有不同失效历程的主要原因。
关键词 ： 环氧涂层,  碳钢,  铝合金,  防腐性能,  电化学阻抗谱    
Abstract：

In this paper, the long-term anticorrosion performance in 3.5%NaCl solution of 10# mild steel and LY12 Al-alloy coated with the same single-component fluorocarbon-modified epoxy coating, was comparatively studied by means of electrochemical tests such as open-circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curve, and macro/micro morphology characterization as well as adhesion test and water contact angle test. The results showed that the modified epoxy coating shows better corrosion resistance when applied on LY12 Al-alloy rather than applied on 10# mild steel by long-term immersion in 3.5%NaCl solution for 3500 h. The failure of the modified epoxy coating on the surface of the two substrates can be divided into four and three stages respectively, and the failure process is different. The corrosion of the coating/metal interface is the key to determine the failure rate of the coating. Low coating adhesion and high water contact angle for the coating on Al-alloy and high coating adhesion and low water contact angle for the coating on carbon steel substrate are the main reasons for the different failure courses of coatings.
Key words： epoxy coating    carbon steel    Al-alloy    corrosion resistance    electrochemical impedance spectroscopy
收稿日期: 2025-02-14      32134.14.1005.4537.2025.046
ZTFLH:  TG174  
基金资助:国家重点研发计划(2022RDC2012502)
通讯作者: 杨延格，E-mail：ygyang@imr.ac.cn，研究方向为金属材料的海洋腐蚀与防护
Corresponding author: YANG Yange, E-mail: ygyang@imr.ac.cn
作者简介: 王 得，女，2000年生，硕士生
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https://www.jcscp.org/CN/10.11902/1005.4537.2025.046      或      https://www.jcscp.org/CN/Y2025/V45/I6/1549

图1  涂层电化学测试用装置示意图
图2  涂覆环氧涂层的10#钢和LY12铝合金开路电位随浸泡时间的变化
图3  涂覆涂层的10#钢4个阶段的Nyquist图和Bode图
图4  涂覆涂层的LY12铝合金3个阶段的Nyquist图和Bode图
图5  用于拟合涂覆涂层的10#钢和LY12铝合金阻抗谱数据的等效电路模型
图6  涂覆涂层的两种金属低频阻抗模值|Z|0.01 Hz随浸泡时间的变化
图7  涂覆涂层的两种金属电化学拟合参数随时间的变化
Time / hRs / Ω·cm2Qc / F·cm-2n1Rc / Ω·cm2Qdl / F·cm-2n2Rct / Ω·cm2W / Ω·cm2σ2
02.96 × 10-42.34 × 10-100.9483.76 × 1010----9.328 × 10-3
21.40 × 10-22.03 × 10-100.9662.79 × 1061.33 × 10-90.4639.80 × 107-9.612 × 10-4
42.89 × 10-43.16 × 10-90.9482.50 × 1062.92 × 10-80.7153.62 × 106-1.237 × 10-3
61.02 × 10-33.42 × 10-100.9406.44 × 1061.28 × 10-80.7836.88 × 106-9.641 × 10-4
121.02 × 10-33.42 × 10-100.9406.44 × 1061.28 × 10-80.7836.88 × 106-4.831 × 10-4
2437.13.28 × 10-100.9469.43 × 1058.66 × 10-80.5862.34 × 106-1.619 × 10-4
481283.35 × 10-100.9471.02 × 1062.14 × 10-70.4871.62 × 106-2.537 × 10-4
7249.23.53 × 10-100.9441.08 × 1067.88 × 10-70.4121.55 × 106-1.001 × 10-4
9640.73.50 × 10-100.9442.60 × 1066.98 × 10-70.4806.76 × 106-5.418 × 10-5
1201093.35 × 10-100.9473.32 × 1066.80 × 10-70.4361.26 × 107-6.914 × 10-5
14468.63.56 × 10-100.9433.74 × 1066.48 × 10-70.3889.29 × 106-3.642 × 10-5
1926843.76 × 10-100.9424.10 × 1052.64 × 10-70.0859.36 × 106-8.478 × 10-4
2407.42 × 10-33.47 × 10-100.9361.20 × 1061.63 × 10-70.3721.25 × 1061.75 × 10-61.923 × 10-4
2881.00 × 10-23.24 × 10-100.9419.01 × 1051.68 × 10-70.3051.47 × 1061.69 × 10-62.082 × 10-4
3363.35 × 10-33.16 × 10-100.9442.28 × 1051.08 × 10-70.2131.87 × 1061.99 × 10-61.623 × 10-4
3841.00 × 10-23.75 × 10-100.9398.34 × 1059.90 × 10-70.3001.41 × 1061.18 × 10-62.102 × 10-5
48030.13.45 × 10-100.9439.43 × 1056.46 × 10-70.3011.90 × 1061.96 × 10-63.349 × 10-5
8164.27 × 10-52.58 × 10-100.9525.61 × 1051.59 × 10-70.1992.04 × 1061.49 × 10-61.492 × 10-4
108076.94.53 × 10-100.9331.13 × 1051.24 × 10-60.3037.79 × 105-4.257 × 10-4
129616.15.98 × 10-100.9181.02 × 1052.88 × 10-60.2655.61 × 105-1.950 × 10-4
15601597.49 × 10-80.7211.10 × 1039.78 × 10-50.4314.20 × 104-3.122 × 10-3
19682944.70 × 10-80.7849.51 × 1029.79 × 10-50.4304.24 × 104-3.152 × 10-3
244871.54.60 × 10-70.6107.77 × 1021.04 × 10-40.5777.37 × 106-3.015 × 10-3
280860.28.07 × 10-70.5824.73 × 1021.47 × 10-40.6931.27 × 104-1.025 × 10-3
314435.61.01 × 10-60.5555.36 × 1022.00 × 10-40.7071.47 × 104-6.570 × 10-4
333661.91.06 × 10-60.5723.91 × 1022.74 × 10-40.6961.25 × 104-9.363 × 10-4
350066.81.23 × 10-60.5703.27 × 1023.30 × 10-40.6981.27 × 104-9.130 × 10-4
表1  10#钢表面涂覆涂层后在3.5%Nacl溶液中得的电化学拟合参数
Time / hRs / Ω·cm2Qc / F·cm-2n1Rc / Ω·cm2Qdl / F·cm-2n2Rct / Ω·cm2W / Ω·cm2σ2
01.00 × 1023.01 × 10-100.9548.63 × 1066.82 × 10-90.8134.00 × 1075.12 × 10-72.87 × 10-3
21.00 × 10-21.00 × 10-90.8712.64 × 1071.88 × 10-90.8758.28 × 1072.50 × 10-81.27 × 10-3
41.00 × 1031.61 × 10-90.8434.13 × 1067.30 × 10-100.9357.10 × 1071.92 × 10-88.37 × 10-4
61.00 × 1022.55 × 10-90.8082.01 × 1067.94 × 10-90.8251.93 × 1071.56 × 10-77.44 × 10-3
121.00 × 10-23.43 × 10-90.7873.25 × 1062.34 × 10-90.9005.82 × 1067.80 × 10-83.23 × 10-3
246.68 × 10-21.62 × 10-90.8491.82 × 1075.44 × 10-90.7507.17 × 1071.02 × 10-74.44 × 10-3
483.31 × 1041.85 × 10-90.8374.82 × 1053.95 × 10-90.8676.10 × 1079.43 × 10-82.72 × 10-3
721.00 × 10-21.41 × 10-90.8593.48 × 1065.27 × 10-90.8108.01 × 1075.70 × 10-83.81 × 10-3
961.00 × 10-26.38 × 10-110.9191.97 × 1057.70 × 10-90.7641.28 × 1085.10 × 10-82.65 × 10-3
1201.00 × 1025.71 × 10-100.9271.51 × 1066.42 × 10-90.8081.34 × 1085.94 × 10-88.24 × 10-4
1681.00 × 1035.59 × 10-100.9326.67 × 1057.84 × 10-90.7869.65 × 1076.85 × 10-82.77 × 10-3
1923.47 × 10-26.58 × 10-100.9216.92 × 1059.09 × 10-90.8256.83 × 1071.01 × 10-51.96 × 10-3
2401.00 × 10-25.82 × 10-100.9291.78 × 1061.20 × 10-80.7739.06 × 1077.26 × 10-83.45 × 10-3
2881.00 × 10-24.86 × 10-100.9431.68 × 1049.68 × 10-90.8498.30 × 1073.92 × 10-81.14 × 10-2
3361.00 × 10-24.57 × 10-90.9491.95 × 1051.24 × 10-80.8046.17 × 1077.65 × 10-87.50 × 10-4
3841.00 × 1033.70 × 10-100.9641.97 × 1051.32 × 10-80.7741.09 × 1086.77 × 10-84.46 × 10-4
4321.00 × 10-23.36 × 10-100.9702.02 × 1072.79 × 10-80.7207.56 × 1072.27 × 10-72.33 × 10-3
4801.00 × 1033.66 × 10-100.9622.81 × 1051.68 × 10-80.7761.00 × 1082.61 × 10-76.33 × 10-4
5761.00 × 10-24.06 × 10-80.9561.57 × 1051.71 × 10-80.7705.11 × 1071.56 × 10-71.51 × 10-3
6961.27 × 10-23.48 × 10-100.9671.04 × 1051.50 × 10-80.7735.91 × 1071.30 × 10-61.60 × 10-3
8161.00 × 10-22.16 × 10-101.0006.62 × 1051.40 × 10-80.7378.80 × 1079.73 × 10-82.68 × 10-3
10801.00 × 10-23.73 × 10-100.9608.76 × 1042.15 × 10-80.8162.28 × 1078.00 × 10-81.22 × 10-3
12961.00 × 10-25.87 × 10-100.9213.42 × 1055.38 × 10-80.8591.72 × 1078.74 × 10-95.80 × 10-3
15601.00 × 10-28.39 × 10-100.8964.80 × 1056.94 × 10-80.8951.02 × 1083.31 × 10-75.05 × 10-3
19681.00 × 1031.72 × 10-90.8485.02 × 1049.05 × 10-80.8776.07 × 1065.18 × 10-71.82 × 10-3
24481.00 × 1034.46 × 10-90.7822.40 × 1041.01 × 10-70.8501.12 × 1073.12 × 10-76.10 × 10-3
28081.00 × 1032.10 × 10-80.6752.21 × 1041.34 × 10-70.8893.80 × 1061.66 × 10-68.04 × 10-3
31441.00 × 1037.92 × 10-90.7452.31 × 1042.94 × 10-70.8814.00 × 1062.42 × 10-68.75 × 10-3
33361.00 × 10-21.66 × 10-90.6922.46 × 1043.49 × 10-70.8642.74 × 1063.05 × 10-69.65 × 10-3
35001.00 × 10-21.70 × 10-80.6932.01 × 1044.08 × 10-70.8451.79 × 1067.18 × 10-89.28 × 10-3
表2  LY12铝合金表面涂覆涂层后在3.5%Nacl溶液中得的电化学拟合参数
图8  涂覆涂层的10#钢和LY12铝合金浸泡3500 h前后的动电位极化曲线
图9  10#钢和LY12铝合金浸泡3500 h前后附着力的测试结果
图10  涂覆涂层的10#钢和LY12铝合金浸泡3500 h前后与水的接触角
图11  涂覆涂层的10#钢浸泡3500 h过程中的宏观形貌演变
图12  涂覆涂层的LY12铝合金浸泡3500 h过程中的宏观形貌演变
图13  涂覆涂层的10#钢和LY12铝合金浸泡3500 h前后的光学显微形貌
图14  涂覆环氧涂层的10#钢和LY12铝合金浸泡3500 h前后的微观形貌
图15  涂覆环氧涂层的10#钢和LY12铝合金浸泡3500 h后的元素分布
图16  涂覆环氧涂层的10#钢和LY12铝合金的失效过程
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