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含有具有pH响应性能的核壳纳米纤维的自修复涂层。

Self-Healing Coatings Containing Core-Shell Nanofibers with pH-Responsive Performance.

作者信息

Wang Qi, Wang Wei, Ji Xiaohong, Hao Xiangping, Ma Chengcheng, Hao Wei, Li Xinglinmao, Chen Shougang

机构信息

School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China.

Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China.

出版信息

ACS Appl Mater Interfaces. 2021 Jan 20;13(2):3139-3152. doi: 10.1021/acsami.0c18933. Epub 2021 Jan 5.

Abstract

The micro-nanofibers prepared by the electrospinning technique can be used as a good container for loading healing agents. The core-shell electrospun nanofibers with polyacrylonitrile as the outer shell and tannic acid (TA) and tung oil as the core healing agents were synthesized by a coaxial electrospinning method and exhibited pH-sensitive ability. The nanofibers as additives were added to an epoxy resin coating as a self-healing coating. The morphological stability of the electrospun nanofibers were observed by a scanning electron microscope and a transmission electron microscope. Fourier transform infrared spectroscopy and fluorescence microscopy reveal that the successful synthesis and uniform distribution of core-shell fibers. The mechanical properties test revealed that the tensile properties of the coating could be improved by adding nanofibers. The infrared mapping test, energy-dispersive spectrometry, and X-ray photoelectron spectroscopy, which were carried out on the scratched part of the coating, proved the release of the healing agent in the damaged part. TA forms a protective film on the exposed metal surface through molecular adsorption under acidic conditions. Meanwhile, the curing of tung oil can effectively compensate into the microcracks to form a TA protective film, which could improve the self-healing performance. As the tung oil dries and solidifies in the alkaline solution, the cross-linking effect of the molecules is combined to form a tight film and strength the self-healing ability. TA as an acidic healing agent and tung oil as an alkaline healing agent played the role of pH-sensitive products in healing the cracked coating. The self-healing rates of coating immersing in 3.5 wt % acidic NaCl solution and alkaline solution were 81.6 and 71.2%, respectively. The composite coating shows a great pH-sensitive self-healing ability to heal the cracked coating.

摘要

通过静电纺丝技术制备的微纳米纤维可作为装载愈合剂的良好载体。采用同轴静电纺丝法合成了以聚丙烯腈为外壳、单宁酸(TA)和桐油为核心愈合剂的核壳结构静电纺纳米纤维,该纳米纤维具有pH敏感能力。将该纳米纤维作为添加剂添加到环氧树脂涂层中制成自愈合涂层。通过扫描电子显微镜和透射电子显微镜观察了静电纺纳米纤维的形态稳定性。傅里叶变换红外光谱和荧光显微镜显示核壳纤维成功合成且分布均匀。力学性能测试表明,添加纳米纤维可提高涂层的拉伸性能。对涂层划痕部位进行的红外映射测试、能谱分析和X射线光电子能谱分析证明了愈合剂在受损部位的释放。TA在酸性条件下通过分子吸附在暴露的金属表面形成保护膜。同时,桐油的固化可有效渗入微裂纹中形成TA保护膜,从而提高自愈合性能。由于桐油在碱性溶液中干燥固化,分子交联作用结合形成致密薄膜,增强了自愈合能力。TA作为酸性愈合剂,桐油作为碱性愈合剂,在修复开裂涂层中发挥了pH敏感产物的作用。涂层浸泡在3.5 wt%酸性NaCl溶液和碱性溶液中的自愈合率分别为81.6%和71.2%。该复合涂层对开裂涂层具有良好的pH敏感自愈合能力。

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