接枝ZnO与单壁碳纳米管协同构筑功能一体化复合涂层

doi:10.6023/A24080230

摘要/Abstract

超疏水涂层因自清洁、防覆冰、耐腐蚀和油水分离等特性, 被众多领域广泛应用. 本研究利用分级分散法和非共价聚乙烯吡咯烷酮(PVP)的位阻作用获得了单分散碳纳米管浆料, 将其作为功能填料制备了氟碳基涂层; 利用ZnO颗粒接枝长烷基链构建了微米级平滑、纳米级粗糙的微/纳结构表面, 其接触角为152.5°, 动态接触角为5°, 实现了功能一体化的仿生超疏水涂层制备. 单分散的单壁碳纳米管(SWCNTs)构成的网络结构与ZnO构成的导电网链协同作用, 使复合涂层具有抗静电性能, 其电阻率为3.15 Ω•m. 涂层的超疏水表面及涂层内部三维交错结构能够延缓腐蚀发生, 复合涂层的腐蚀电流密度为9.66×10⁻⁸A/cm², 比Q235钢低3个数量级. 同时该涂层具有良好的机械稳定性和耐酸碱性, 兼备了抗静电、耐腐蚀、自清洁功能一体化特性.

关键词: 微/纳结构, 超疏水涂层, 抗静电性能, 耐腐蚀性, 自清洁性能

Superhydrophobic coatings are widely used in many fields because of their self-cleaning, anti-icing, anti- corrosion and oil-water separation properties. Conventionally, superhydrophobicity is deﬁned as possessing a water contact angle above 150° and a sliding angle below 10°. A superhydrophobic surface is produced either by creating a rough surface on a hydrophobic material or by modifying a rough surface using materials having a low surface free energy. To consider the practical application of superhydrophobic coating, we prepared a micro-nanoscale flowerlike superhydrophobic coating using a surface treatment method. In our work, the monodisperse single-walled carbon nanotubes (SWCNTs) can be obtained using a non-covalent polyvinylpyrrolidone (PVP) dispersant under the graded homogenization method. We incorporate low amounts of 0.15% (w) SWCNTs into fluorocarbon (FC) coatings to fabricate composite coatings. The micro-nano structure surface with micron level smooth and nanometer level rough was constructed by ZnO particles after surface treatment. The contact angle of composite coating was 152.5° and a sliding angle was 5°, and the bionic superhydrophobic coating with integrated functions was fabricated. The result suggests that the combination of the rough structures achieved by the flower-like ZnO and low surface energy provided by stearic acid modiﬁcation results in superhydrophobicity and a very low sliding angle. The network structure formed by SWCNTs and the conductive grid chain formed by ZnO has decided the antistatic properties, the resistivity is 3.15 Ω•m. The superhydrophobic surface and the three-dimensional cross-structure of the ZnO/SWCNTs/FC composite coating can delay the corrosion. The corrosion current density of the composite coating is 9.66×10⁻⁸ A/cm², which is 3 orders of magnitude lower than that of Q235 steel. The ZnO/SWCNTs/FC composite coating could be easily repaired after losing superhydrophobicity by surface treatment. At the same time, the coating has good mechanical stability, acid and alkali resistance, and the integrated characteristics of electrical resistance, corrosion resistance and self-cleaning functions. These coatings can ﬁnd potential applications in the industry.

Key words: micro-nano structure, superhydrophobic coatings, antistatic property, corrosion resistance, self-cleaning property

引用此文

满田囡, 王芷琦, 邢月, 马克明, 农智升, 卢少微. 接枝ZnO与单壁碳纳米管协同构筑功能一体化复合涂层[J]. 化学学报, 2024, 82(11): 1142-1149.

Tiannan Man, Zhiqi Wang, Yue Xing, Keming Ma, Zhisheng Nong, Shaowei Lu. Multifunctional Integrated Composite Coatings Based on both Grafted-ZnO and Single-walled Carbon Nanotubes[J]. Acta Chimica Sinica, 2024, 82(11): 1142-1149.

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图/表 9

图1. 复合涂层的红外光谱图

Figure 1. FTIR spectra of composite coatings

图2. ZnO/SWCNTs/FC复合涂层的X射线光电子能谱

Figure 2. XPS of ZnO/SWCNTs/FC composite coatings

图3. 复合涂层的扫描电子显微镜图

Figure 3. SEM images of composite coatings (a) SWCNTs/FC coating, (b) non-modified ZnO/SWCNTs/FC coating, (c) 5% (w) ZnO/SWCNTs/FC coating, (d) 10% (w) ZnO/SWCNTs/FC coating, (e) 12.5% (w) ZnO/SWCNTs/FC coating, (f) 15% (w) ZnO/SWCNTs/FC coating

w(ZnO)/%	电导率/(S•cm⁻¹)	电阻率/(Ω•m)
0	0.27	0.05
5	2.57×10⁻³	3.89
10	1.61×10⁻³	6.23
12.5	3.29×10⁻³	3.15
15	7.14×10⁻³	1.43

表1. 复合涂层的电阻率

Table 1. Resistivity of the composite coatings

图4. 复合涂层的接触角

Figure 4. Contact angle of composite coatings

图5. 复合涂层的(a)极化曲线, (b)阻抗图, (c)频率阻抗图和(d) Bode图

Figure 5. (a) Polarization curves, (b) plane impedance, (c) modulus impedance and (d) phase angle of composite coating

图6. (a)剪切砂纸磨损法; (b)磨损过程接触角的变化; (c)修复后涂层的表面; (d)不同酸碱性的液滴状态

Figure 6. (a) Shear abrasive wear method; (b) contact angles after shear abrasive; (c) the repaired surface; (d) acidity and alkalinity measurement

图7. 复合涂层的自清洁测试

Figure 7. Self-cleaning measurement of the composite coatings

图8. 复合涂层的耐腐蚀和抗静电机理图

Figure 8. Corrosion resistance and anti-static mechanism of composite coating

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