Preparation of covalently functionalized graphene superhydrophobic anticorrosive composite coating materials
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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Icorr最低(8.872×10−9 A/cm2)，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。Abstract: 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 Icorr of the prepared composite coating with fluorinated graphene content of 0.5wt% is the lowest (8.872×10−9 A/cm2), 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.
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Key words:
- graphene /
- functionalization /
- superhydrophobicity /
- composite coating /
- anticorrosion
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图 1 超疏水改性石墨烯复合材料(FAGO)制备示意图
Figure 1. Schematic illustration of the preparation procedures for superhydrophobic modified graphene composites (FAGO)
图 3 氧化石墨烯(GO)、炔基化氧化石墨烯(AGO)和FAGO的FTIR图谱
Figure 3. FTIR spectra of graphene oxide (GO), alkynylated graphene oxide (AGO) and FAGO
图 7 PFOMA含量不同的FAGO的水接触角
Figure 7. Water contact angles of the FAGO with different PFOMA contents (PFOMA∶St=1∶9, 3∶7, 5∶5, 7∶3, 9∶1)
图 8 不同表面涂覆FAGO时的水接触角
Figure 8. Water contact angles of the FAGO attached to different surfaces
图 9 FAGO0.5wt%/EP ((a)、(d)、(g))、FAGO1.0wt%/EP ((b)、(e)、(h)) 和FAGO1.5wt%/EP ((c)、(f)、(i)) 的SEM图像
Figure 9. SEM images of FAGO0.5wt%/EP ((a), (d), (g)), FAGO1.0wt%/EP ((b), (e), (h)) and FAGO1.5wt%/EP ((c), (f), (i))
图 10 FAGO含量不同的FAGO/环氧树脂复合涂层的水接触角
Figure 10. Water contact angles of FAGO/epoxy resin composite coating with different FAGO contents
图 11 45#碳钢涂覆蜡、FAGO0.5wt%/EP、FAGO1.0wt%/EP和FAGO1.5wt%/EP复合涂层的Tafel曲线
Figure 11. Tafel curves of 45# carbon steel with wax, FAGO0.5wt%/EP, FAGO1.0wt%/EP and FAGO1.5wt% /EP composite coatings
图 12 45#碳钢涂覆FAGO0.5wt%/EP试样的Nyquist图
Figure 12. Nyquist plots of 45# carbon steel samples coated with FAGO0.5wt%/EP
图 13 45#碳钢涂覆FAGO0.5wt%/EP试样的Bode图
Figure 13. Bode plots of 45# carbon steel samples coated with FAGO0.5wt%/EP
图 14 涂覆FAGO0.5wt%/EP的45#碳钢试样在人工模拟海水中浸泡1天、25天和55天及在酸液中浸泡25天、70天后的光学照片
Figure 14. Optical photos of 45# carbon steel samples coated with FAGO0.5wt%/EP after soaking in artificial simulated seawater for 1 day, 25 days and 55 days, and soaking in acid solution for 25 days and 70 days
图 15 FAGO/EP复合涂层的防腐机制模型
Figure 15. Anticorrosion mechanism model of FAGO/ EP composite coating
表 1 涂覆涂层的45#碳钢在3.5wt% NaCl溶液中通过Tafel极化曲线拟合得到的腐蚀参数
Table 1. Fitting corrosion data of coated 45# carbon steel samples in 3.5wt% NaCl solution by Tafel polarization curves
Sample Ecorr/V Icorr/(a·cm−2) ba/(V·dec−1) bc /(V·dec−1) vcorr/(mm·year−1) Wax −0.284 1.665×10−6 7.801 −11.732 1.932×10−2 FAGO0.5wt%/EP −0.206 8.872×10−9 16.890 −13.401 1.032×10−4 FAGO1.0wt%/EP −0.226 1.999×10−8 12.817 −13.913 2.327×10−4 FAGO1.5wt%/EP −0.231 2.111×10−7 4.583 −4.905 2.454×10−3 Notes: Corrosion current density (Icorr), anodic Tafel slope (ba ), corrosion potential (Ecorr), corrosion rate (vcorr) and cathodic Tafel slope (bc) were calculated via electrochemical analyzer instrument. 
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