碱刻蚀埃洛石微米管负载2-巯基苯并噻唑并包覆壳聚糖防腐蚀自修复涂层  

Corrosion Resistance of Alkali-etched Hollow Halloysite Microtubes Loaded with 2-Mercaptobenzothiazole and Encapsulated with Chitosan for Self-healing Coatings

作　　者：石浩[1] 王志豪 褚贵文 张培琦 刘润远 王艺翔 孙雷 宋立英 蒋全通 麻福斌 SHI Hao;WANG Zhihao;CHU Guiwen;ZHANG Peiqi;LIU Runyuan;WANG Yixiang;SUN Lei;SONG Liying;JIANG Quantong;MA Fubin(College of Mechanical and Electronic Engineering,Shandong University of Science and Technology,Qingdao 266590,China;College of Safety and Environmental Engineering,Shandong University of Science and Technology,Qingdao 266590,China;Institute of Oceanology,Chinese Academy of Sciences,Qingdao 266071,China)

机构地区：[1]山东科技大学机械电子工程学院,青岛266590 [2]山东科技大学安全与环境工程学院,青岛266590 [3]中国科学院海洋研究所,青岛266071

出　　处：《中国表面工程》2025年第1期127-140,共14页China Surface Engineering

基　　金：山东省自然科学基金面上项目(ZR2021ME087);山东省重点研发计划(竞争性创新平台)(2023CXPT062)。

摘　　要：目前大多数无机微纳米载体在有机涂层中存在团聚问题,对自修复涂层的防腐蚀性能和使用寿命有一定影响。对碱刻蚀埃洛石微米管(HMTs)负载缓蚀剂2-巯基苯并噻唑(MBT),并通过外包覆壳聚糖(CS)作为微米填料,制备填料在涂层良好分散性和缓蚀剂高负载量的自修复涂层。通过傅里叶变换红外光谱(FTIR)证实HMTs成功负载MBT,且缓蚀剂的防腐功能没有失效。使用扫描电镜图(SEM)和透射电镜图(TEM),观察HMTs、HMTs负载MBT(HMTs-MBT)和包覆CS的HMTs-MBT(CS-HMTs-MBT)的外貌结构。通过热重分析(TGA),测得HMTs对MBT的质量负载约为13wt.%,HMTs外包覆CS的质量分数约为61 wt.%。通过测试各样品在聚二甲基硅氧烷(PDMS)涂层中分散状况,证明包覆CS可以提高微纳米容器在涂层中的分散性。使用电化学阻抗谱(EIS)来评估涂层的自修复能力,通过分析|Z|_(=0.01Hz)值确定在第4 d自修复涂层的自修复能力达到峰值,使用ZSimpWin对获得的阻抗数据进行拟合,验证自修复涂层对金属的防腐蚀能力。在4 d浸泡试验结束后,通过SEM、电镜能谱(EDS)测试和X射线光电子能谱(XPS),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,表明涂层划痕处已被缓蚀剂修复。利用CS在有机涂层中良好分散特性,增强CS-HMTs-MBT在PDMS涂层中的分散性。当涂层有划伤时,缓蚀剂MBT被释放并吸附在金属表面形成紧密薄膜隔绝腐蚀性物质,实现涂层对破损处自主修复。具有高分散性的CS-HMTs-MBT复合自修复涂层为金属设备的防腐蚀涂层提供了新的解决方案,有望在海洋工程和其他相关领域得到广泛应用,从而减少损失并延长设备的寿命。Metal equipment is vulnerable to corrosion when used in harsh marine environments.The speed,fuel consumption,and service life of marine equipment are greatly reduced owing to seawater corrosion,which results in significant economic losses every year,severely impeding the development of the national economy.Therefore,protecting marine equipment from corrosion damage has always been an urgent issue.Currently,coating technology is one of the most effective and commonly used methods for protecting metals from corrosion.Preparing self-healing coatings with better performance by adding micromaterials and nanomaterials to the coatings and further improving the corrosion protection ability of the coatings has recently become an important research direction for metal protective coatings.However,most inorganic microcarriers and nanocarriers have agglomeration problems in organic coatings,which affects the corrosion resistance and service life of self-healing coatings.In this study,the natural halloysite microtube(HMT)was reamed by alkali etching to increase its inner diameter.Secondly,the corrosion inhibitor,2-mercaptobenzothiazole(MBT),was loaded into alkali-etched halloysite microtubes(HMTs)by vacuum adsorption in a vacuum chamber.Then,chitosan(CS)was coated on the outer surface of HMTs under acidic conditions to prepare micron fillers with a corrosion inhibition function.Finally,micron fillers were added to the PDMS coating at the rate of 15 wt.%and fully stirred to prepare the self-healing coating.Fourier-transform infrared spectroscopy(FTIR)was used to confirm the successful loading of MBT into HMTs,and the corrosion inhibition function of the inhibitor remained effective.Scanning electron microscopy(SEM)and transmission electron microscopy(TEM)were employed to observe the morphological structures of HMTs,HMTs-MBT,and CS-HMTs-MBT.Through thermal gravimetric analysis(TGA),HMTs were shown to carry approximately 13 wt.%of MBT,and HMTs encapsulated with CS accounted for approximately 61 wt.%by mass.The dispersion of vario

关 键 词：碱刻蚀埃洛石微米管 2-巯基苯并噻唑 壳聚糖 分散性 自修复涂层 

分 类 号：TG176[金属学及工艺—金属表面处理]