碱刻蚀埃洛石纳米管装载<strong>2-</strong>巯基苯并噻唑自修复涂层的制备和性能

doi:10.11901/1005.3093.2024.262

材料研究学报

2025, Vol. 39

Issue (5): 377-388 DOI: 10.11901/1005.3093.2024.262

研究论文

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碱刻蚀埃洛石纳米管装载2-巯基苯并噻唑自修复涂层的制备和性能

包继华¹, 武鹏¹, 张浩然¹, 褚贵文¹, 宋立英¹(

), 蒋全通², 麻福斌²

^1.山东科技大学青岛 266590
^2.中国科学院海洋研究所青岛 266071

Self-healing Performance of a Novel Coating Composed of Polydimethylsiloxane Matrix and Surface Modified Halloysite Nanotubes Filler

BAO Jihua¹, WU Peng¹, ZHANG Haoran¹, CHU Guiwen¹, SONG Liying¹(

), JIANG Quantong², MA Fubin²

^1.Shandong University of Science and Technology, Qingdao 266590, China
^2.Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China

引用本文:

包继华, 武鹏, 张浩然, 褚贵文, 宋立英, 蒋全通, 麻福斌. 碱刻蚀埃洛石纳米管装载2-巯基苯并噻唑自修复涂层的制备和性能[J]. 材料研究学报, 2025, 39(5): 377-388.
Jihua BAO, Peng WU, Haoran ZHANG, Guiwen CHU, Liying SONG, Quantong JIANG, Fubin MA. Self-healing Performance of a Novel Coating Composed of Polydimethylsiloxane Matrix and Surface Modified Halloysite Nanotubes Filler[J]. Chinese Journal of Materials Research, 2025, 39(5): 377-388.

全文: PDF(11907 KB) HTML

摘要:

将Cu作为腐蚀基材，采用聚二甲基硅氧烷涂料(加入定量固化剂)作为涂层主体，在涂层中加入一种碱刻蚀埃洛石纳米管(HNTs)装载2-巯基苯并噻唑(MBT)并在表面包覆壳聚糖和聚乙二醇共聚物(CP)的纳米填料，制备一种自修复涂层，浸泡在3.5% (质量分数)的NaCl溶液中。用傅立叶红外吸收光谱(FTIR)、热重分析(TGA)、扫描电子显微镜、电化学阻抗谱(EIS)、Kelvin探针和UV吸收光谱等手段对其表征，研究了这种自修复涂层的性能。结果表明：HNTs装载MBT并被CP成功包覆，HNTs对MBT的装载量(质量分数)为12%；扫描电子显微镜、EIS阻抗、Kelvin探针和UV吸收光谱证明了这种HNTs (CP-HNTs-MBT)涂层的自修复性能良好并能实现二次自修复。可见，CP-HNTs-MBT涂层的防腐蚀性能较强，具有至少两次以上的循环自修复能力。这种涂层对金属材料的保护性能较好。

关键词 ：有机高分子材料, 壳聚糖, 聚乙二醇, 碱刻蚀埃洛石纳米管, 2-巯基苯并噻唑, 循环自修复涂层

Abstract：

Herein, halloysite nanotubes (HNTs) as typical micro-nano carrier were alkali etched to expand their aperture, then, on their surface 2-mercaptobenzothiazole (MBT) was deposited, and finally chitosan-polyethylene glycol copolymer (CP) was coated as top surface layer, thus a new filler of surface modified HNTs was made. Next, a novel self-healing coating (CP-HNTs-MBT) is developed with polydimethylsiloxane (PDMS) as matrix and the surface modified HNTs as filler etc., and then the coating is applied on Cu substrate. The structure and composition of the filler and the corrosion performance, especially its re-healing capacity in 3.5% NaCl solution of the coating are assessed via Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), UV absorption spectroscopy, immersion test, and Kelvin probe etc. Results indicate that MBT is successfully loaded onto HNTs, achieving a loading capacity of 12% by mass. The results of SEM, EIS, Kelvin probe, and UV absorption spectroscopy confirm the excellent self-healing performance of the CP-HNTs-MBT coating, which can still show significant self-healing ability, even when it is used for second time. It follows that the CP-HNTs-MBT coating exhibits strong corrosion resistance, with the ability to maintain self-healing ability for multiple cycle usage, thereby providing effective protection for metal materials.

Key words： organic polymer materials chitosan polyethylene glycol alkaline etched halloysite nanotubes 2-mercaptobenzothiazole cyclic self-healing coating

收稿日期: 2024-06-12

ZTFLH:

TG176

基金资助:山东省自然科学基金(ZR2021ME087);十四五国家重点研发计划(2023YFC2907304);14th Five Year National Key R & D Program Project(2023YFC2907304)

通讯作者: 宋立英，songliying0520@163.com，研究方向为金属腐蚀与防护

Corresponding author: SONG Liying, Tel: (0532)86081281, E-mail: songliying0520@163.com

作者简介: 包继华，男，1971年生，副教授

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图1 CP-HNTs-MBT涂层的制备步骤

图2 HNT、HNTs、MBT和HNTs-MBT的傅立叶红外光谱

图3 CS、PEG、CP-HNTs-MBT和HNTs-MBT的傅立叶红外光谱

图4 HNTs、MBT、HNTs-MBT和CP-HNTs-MBT的TGA分析

图5 HNT 、HNTs、HNTs-MBT、CP-HNTs-MBT的SEM照片以及HNTs和CP-HNTs-MBT的TEM照片

图6 CP-HNTs-MBT涂层和空白涂层上的划痕在3.5% NaCl溶液中的阻抗模量(f = 0.01 Hz)

图7 在3.5% NaCl溶液中浸泡0、8、16、24和30 d后CP-HNTs-MBT涂层和空白涂层上划痕的Nyquist和Bode图

图8 等效电路模型

表1 在3.5% NaCl溶液中浸泡0 d，8 d，16 d，24 d，30 d后CP-HNTs-MBT涂层的拟合阻抗参数

表2 在3.5% NaCl溶液中浸泡0 d，8 d，16 d，24 d，30 d后空白涂层的拟合阻抗参数

图9 CP-HNTs-MBT划痕涂层在3.5% NaCl溶液中浸泡0 d、4 d、6 d和8 d后的SKP电位分布

图10 浸入3.5% NaCl溶液中的含CP-HNTs-MBT涂层上的划痕在0 d和8 d后的SEM图像和EDS数据

图11 CP-HNTs-MBT划痕涂层在3.5% NaCl溶液中浸泡0 d、4 d、6 d和8 d后的SVET电流密度分布

图12 pH = 5和pH = 7的MBT标准浓度曲线

图13 在pH值为5、7条件下MBT释放量与时间的关系

图14 pH = 5、pH = 7的MBT在不同释放时间的UV光谱

图15 腐蚀机理和自修复机理示意图

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