包继华,张浩然,王志豪,武鹏,宋立英,蒋全通,麻福斌.多功能埃洛石纳米管防腐蚀超疏水自修复涂层[J].表面技术,2025,54(8):74-83, 135.
BAO Jihua,ZHANG Haoran,WANG Zhihao,WU Peng,SONG Liying,JIANG Quantong,MA Fubin.Multifunctional Halloysite Nanotube Anti-corrosion Superhydrophobic Self-healing Coating[J].Surface Technology,2025,54(8):74-83, 135 |
| 多功能埃洛石纳米管防腐蚀超疏水自修复涂层 |
| Multifunctional Halloysite Nanotube Anti-corrosion Superhydrophobic Self-healing Coating |
| 投稿时间：2024-06-05 修订日期：2024-08-01 |
| DOI：10.16490/j.cnki.issn.1001-3660.2025.08.006 |
| 中文关键词: 碱刻蚀埃洛石纳米管 苯并三氮唑 十八烷基三甲氧基硅烷 超疏水 自修复涂层 |
| 英文关键词:alkali-etched halloysite nanotubes benzotriazole octadecyltrimethoxysilane superhydrophobic self-healing coating |
| 基金项目:山东省自然科学基金(ZR2021ME087);十四五国家重点研发计划项目(2023YFC2907304) |
| 作者 | 单位 |
| 包继华 | 山东科技大学，山东 青岛 266590 |
| 张浩然 | 山东科技大学，山东 青岛 266590 |
| 王志豪 | 山东科技大学，山东 青岛 266590 |
| 武鹏 | 山东科技大学，山东 青岛 266590 |
| 宋立英 | 山东科技大学，山东 青岛 266590 |
| 蒋全通 | 中国科学院海洋研究所，山东 青岛 266071 |
| 麻福斌 | 中国科学院海洋研究所，山东 青岛 266071 |
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| Author | Institution |
| BAO Jihua | Shandong University of Science and Technology, Shandong Qingdao 266590, China |
| ZHANG Haoran | Shandong University of Science and Technology, Shandong Qingdao 266590, China |
| WANG Zhihao | Shandong University of Science and Technology, Shandong Qingdao 266590, China |
| WU Peng | Shandong University of Science and Technology, Shandong Qingdao 266590, China |
| SONG Liying | Shandong University of Science and Technology, Shandong Qingdao 266590, China |
| JIANG Quantong | Institute of Oceanology Chinese Academy of Sciences, Shandong Qingdao 266071, China |
| MA Fubin | Institute of Oceanology Chinese Academy of Sciences, Shandong Qingdao 266071, China |
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| 中文摘要: |
| 目的 延缓金属腐蚀，提高涂层使用寿命。方法 通过对碱刻蚀埃洛石纳米管(HNTs)负载缓蚀剂苯并三氮唑(BTA)，并采用十八烷基三甲氧基硅烷(OTMS)对HNTs外表面进行改性，将改性后的HNTs作为纳米填料，制备了一种具有超疏水能力的自修复防腐涂层。结果 通过傅里叶变换红外光谱(FTIR)证实HNTs成功负载了缓蚀剂BTA、外表面成功添加了OTMS;通过热重分析(TGA)，证明了BTA的负载以及OTMS的包覆;通过光学接触角测量仪测得涂层的水接触角为153°，证明涂层具有超疏水性能;使用电化学阻抗(EIS)分析涂层的自修复能力，当涂层被划伤后，划痕处HNTs破损，缓蚀剂BTA被释放并通过强电化学吸附与铜基体结合，形成一层保护膜，通过分析自修复涂层的阻抗模值得出在第6天涂层的自修复能力达到最大，使用ZSimpWin对实验的阻抗数据进行拟合，证实了涂层具有自修复能力;通过SEM、EDS测试，得出自修复涂层划痕处铜元素含量大幅降低，利用扫描Kelvin探针(SKP)测试发现划痕处电势谷消失，表明划痕已被缓蚀剂所修复。结论 制备的OTMS-HNTs-BTA自修复超疏水涂层能够有效防止液体的附着并且具有自修复能力，可有效延长涂层的使用寿命。 |
| 英文摘要: |
| At present, coating technology is widely used in metal corrosion protection. For traditional anticorrosive coatings, when the coating is damaged due to external interference, the bare metal matrix at the scratch will be corroded, and the corrosive substances attached to the surface of the coating will also accelerate the failure of the coating to a certain extent, resulting in metal corrosion. In this paper, a self-healing anticorrosive coating with superhydrophobic ability is prepared with alkali-etched nanotubes (HNTs) modified with corrosion inhibitor benzotriazole (BTA) and octadecyl trimethoxysilane (OTMS) as nano-filler. The comparison of BTA, HNTs and HNTS-BTA by Fourier transform infrared spectroscopy (FTIR) confirms that HNTs successfully load the corrosion inhibitor BTA, and the comparison of HNTS-BTA and OTMS-HNTS-BTA confirms that OTMS is successfully added to the outer surface. The successful loading of BTA and the coating of OTMS are proved by thermogravimetric analysis (TGA). The water contact angle of the OTMS-HNTs-BTA coating is 153°, while that of the HNTs-BTA coating is 103° and that of the blank coating is 77°. It is proved that the OTMS-HNTs-BTA coating has super hydrophobic properties and friction experiments show that the coating has certain wear resistance. Electrochemical impedance (EIS) is used to analyze the self-healing ability of the coating. When the coating is scratched, the HNTs at the scratch are damaged, and the corrosion inhibitor BTA is released and bonded with the copper matrix through strong electrochemisorbed to form a protective film. By analyzing the impedance mode value of the self-healing coating, the self-healing ability of the coating reaches the maximum on the 6th day. The impedance data of the experiment are fitted with ZSimpWin, and the self-healing ability of the coating is confirmed. By observing the surface morphology of HNTs-BTA and OTMS-HNTS-BTA, it can be seen that the morphology and structure of Halloysite nanotubes are not changed after alkali etching and surface modification, and a thin film is formed on the outer surface after OTMS modification. According to SEM and EDS tests, the content of copper in the scratches of the repaired coating is significantly reduced. When scratches are produced, the content of copper is about 72.9%, while when soaked in 3.5wt.% NaCl solution for 6 d, the content of copper in the scratches is reduced to 3.4%, indicating that the scratches are successfully repaired. The coating release inhibitor successfully covers the metal surface to form a protective film. The scanning Kelvin probe (SKP) test finds that the potential valley at the scratch gradually decreases with time and disappears at the 6th day, indicating that the scratch is repaired by the corrosion inhibitor, and the repair effect reaches the best at the 6th day. By alkali etching of alloxite nanotubes, loading corrosion inhibitor BTA and surface modification on the outer surface of alloxite using OTMS, the modified alkali-etched alloxite nanotubes with corrosion inhibitor are blended with epoxy resin. The prepared OTMS-HNTs-BTA coating can effectively prevent the adhesion of corrosive substances and has self-healing ability when the coating is damaged, which can effectively protect the metal surface and extend the service life of the coating. |
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