共价功能化石墨烯超疏水防腐复合涂层材料的制备  

Preparation of covalently functionalized graphene superhydrophobic anticorrosive composite coating materials

作　　者：刘刚 欧宝立 赵欣欣[1] 彭彩茹 汪雨微 LIU Gang;OU Baoli;ZHAO Xinxin;PENG Cairu;WANG Yuwei(School of Materials Science and Engineering,Hunan University of Science and Technology,Xiangtan 411201,China;State Key Laboratory of Tribology,Tsinghua University,Beijing 100084,China;Hunan Provincial Key Defense Laboratory of High Temperature Wear-Resisting Materials and Preparation Technology(Hunan University of Science and Technology),Xiangtan 411201,China;Hunan Provincial Key Lab of Advanced Materials for New Energy Storage and Conversion(Hunan University of Science and Technology),Xiangtan 411201,China;Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers(Hunan University of Science and Technology),Xiangtan 411201,China)

机构地区：[1]湖南科技大学材料科学与工程学院,湘潭411201 [2]清华大学摩擦学国家重点实验室,北京100084 [3]高温耐磨材料及制备技术湖南省国防科技重点实验室(湖南科技大学),湘潭411201 [4]新能源储存与转换先进材料湖南省重点实验室(湖南科技大学),湘潭411201 [5]精细聚合物可控制备及功能应用湖南省重点实验室(湖南科技大学),湘潭411201

出　　处：《复合材料学报》2021年第10期3236-3246,共11页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金面上项目(51775183);清华大学摩擦学国家重点实验室开放基金(SKLTKF17B14);国家级大学生创新创业项目(S202010534001S);湖南省普通高等学校教学改革研究项目(湘教通[2019]291号);湖南省大学生创新创业项目(S202010534033)。

摘　　要：石墨烯/有机聚合物复合涂层材料较纯聚合物材料具有更优越的阻隔性能,然而由于石墨烯之间高表面能和分子间作用力,使石墨烯在防腐等领域的应用潜力无法充分发挥。本文首先以传统自由基共聚方法合成一种含氟丙烯酸酯共聚物,并采用丙炔胺对氧化石墨烯改性合成炔基化氧化石墨烯,然后利用含氟丙烯酸酯共聚物末端氰基通过点击化学反应以共价键形式接枝在炔基化氧化石墨烯表面。疏水性分析表明,含氟共聚物功能化石墨烯的水接触角达到153°,将制备的功能化石墨烯涂敷于钢板基体时,水接触角提高到171.3°。扫描电镜显示,在炔基化石墨烯表面生长有大量300-600 nm的半球形接枝物。同时,将含氟共聚物功能化石墨烯/环氧树脂复合材料应用于碳素结构钢中,通过Tafel曲线和电化学阻抗谱对其耐蚀性能进行表征。结果显示,氟化石墨烯含量为0.5wt%的复合涂层的电流密度I_(corr)最低(8.872×10^(-9)A/cm^(2)),比其他涂层样品低1-2个数量级。综上所述,本实验所制备的涂层材料具有良好的防腐性能,这一研究为开发石墨烯防腐蚀涂层材料提供了一种新的策略。Graphene/organic polymeric composite coating materials have superior barrier properties compared with pure polymeric materials.However,due to high surface energy and intermolecular force between graphene,the potential application of graphene in anticorrosion and other fields is limited.In this paper,a fluorinated acrylate copolymer was synthesized by conventional free radical copolymerization,and then acetylized graphene oxide was synthesized by modifying graphene oxide with propargylamine.Then,the terminal cyano group of fluorinated acrylate copolymer was grafted onto the surface of acetylized graphene oxide by covalent bond through click chemistry reaction.Hydrophobicity analysis indicates that the water contact angle of the fluorine-containing copolymer functionalized graphene is 153°,and the water contact angle is increased to 171.3°when the prepared functionalized graphene is applied to the steel-plate substrate.The scanning electron microscope indicates that the 300-600 nm hemispherical grafted part is grown on the alkynylated-graphene surface.The fluorine-containing copolymer functionalized graphene/epoxy resin composites are applied to the carbon structural steel,and the corrosion protection performance is characterized by both Tafel curves and electrochemical impedance spectroscopy.The results show that the current density I_(corr)of the prepared composite coating with fluorinated graphene content of0.5 wt%is the lowest(8.872×10^(-9)A/cm^(2)),which is 1-2 orders of magnitude lower than that of other coating samples.In summary,the coating materials prepared in this experiment have excellent anticorrosion properties.This research provides a new strategy for the development of graphene anticorrosion coating materials.

关 键 词：石墨烯 功能化 超疏水 复合涂层 防腐蚀 

分 类 号：TQ174.75[化学工程—陶瓷工业]