Preparation and properties of wear-resistant superhydrophobic coatings based on SiO2/ aramid nanofibers "grape" structure
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摘要: 超疏水材料由于其超高的防水性在工业防腐等领域展现出巨大的应用前景，然而在实际使用过程中，涂层表面的微纳结构和低表面能物质会被不断损耗从而影响超疏水性能。本文主要以聚多巴胺(PDA)包裹的芳纶纳米纤维(ANFs)作为一种微纳米构筑单元，在其上通过溶胶凝胶法原位生长纳米SiO2，并通过对其进行低表面能改性构建“葡萄”形超疏水结构，最后通过“粘接剂-超疏水粒子”喷涂得到超疏水涂层。当正硅酸乙酯(TEOS)添加量为2.1wt%时，超疏水涂层的接触角(WCA)为158°±1.5°。所制得的涂层具有良好的力学性能，在分别经过200 g砝码在25 μm砂纸下的240次磨损和400 g砂冲实验，仍能保持良好的超疏水性能。通过Nyquist测试表明样片阻抗弧明显变大、Tafel测试表明腐蚀电位正移，喷涂超疏水涂层后能够有效提升防腐性能。Abstract: Hydrophobic materials have shown great potential in industrial corrosion prevention due to their extremely high waterproofing properties. However, in practical applications, the micro-nano structure and low surface energy of the coating surface are continuously worn away, affecting the superhydrophobic performance. This study focuses on using polydopamine (PDA) coated aramid nanofibers (ANFs) as micro-building units to grow nano-SiO2 through sol-gel condensation and construct a "grape-like" superhydrophobic structure through low surface energy modification. Finally, a superhydrophobic coating is obtained by spray-coating with a "binder-superhydrophobic particles" mixture. When the ethyl orthosilicate (TEOS) addition is 2.1wt%, the contact angle of the superhydrophobic coating is 158°±1.5°, respectively. The resulting coating exhibits good mechanical properties and maintains its superhydrophobic performance even after undergoing 240 cycles of abrasion on 25 μm sandpaper with a 200 g weight and a sand erosion test with a 400 g load. Nyquist testing shows a significant increase in impedance arc, and Tafel testing indicates a positive shift in corrosion potential, demonstrating that the spray-coated superhydrophobic coating can effectively enhance corrosion resistance.
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Key words:
- superhydrophobicity /
- aramid nanofibers /
- polydopamine /
- SiO2 /
- coating /
- mechanical properties
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图 1 “葡萄”形SiO2/ANFs-PDA(SAP)超疏水粒子制备流程图
Figure 1. "Grape-like" SiO2/ANFs-PDA(SAP) superhydrophobic particle preparation process diagram
ANFs—Aramid nanofibers; PDA—Polydopamine; TEOS—Ethyl orthosilicate
图 2 SAP中不同TEOS的添加量的接触角(WCA)和滚动角(SCA)
Figure 2. Water contact angle (WCA) and slide contact angle (SCA) of SAP with different addition amounts of TEOS
图 3 (a-b) ANF的TEM图;(c-d) ANFs-PDA的SEM图; (e-f) TEOS含量为2.1%SAP的SEM图
Figure 3. (a-b) TEM images of ANF; (c-d) SEM images of ANFs-PDA; (e-f) SEM images of SAP with a TEOS content of 2.1%
图 4 (a) ANFs的FTIR全反射谱图; (b) ANFs-PDA和SAP的FTIR谱图
Figure 4. (a) Total reflection FTIR spectra of ANFs; (b) FTIR of ANFs-PDA and SAP
图 5 (a) ANFs的XPS C1s谱图; (b) ANFs-PDA的XPS C1s谱图; (c) SAP的XPS C1s谱图
Figure 5. (a) XPS C1s spectrum of ANFs; (b) XPS C1s spectrum of ANFs-PDA; (c) XPS C1s spectrum of SAP
图 6 水、茶、牛奶、空压油、菜籽油、正十六烷在涂层上静置10 min后的图像
Figure 6. Images of water, tea, milk, air-compressor-oils, Rapeseed oil and hexadecane he-xadecane on the coating for 10 minutes
图 7 预固化时间分别为15 min(a)、20 min(b)、25 min(c)的SAP涂层横截面的SEM图像
Figure 7. SEM images of the cross section of SAP coatings with pre-curing times of 15 min(a), 20 min(b), and 25 min(c)
图 8 不同底层预固化时间的超疏水涂层表面的元素分布图: (a)预固化时间为20 min; (b)预固化时间为24 min
Figure 8. Element distribution maps on the surface of superhydrophobic coatings with different pre-curing times at the bottom layer (a): the pre curing time is 20 minutes; (b) the pre curing time is 24 minutes
图 9 (a) SAP涂层在200 g砝码25 μm砂纸磨损下的WCA和SCA; (b) ASF涂层在200 g砝码25 μm砂纸磨损下的WCA和SCA; (c)落砂实验示意图;(d)SAP涂层随落砂磨损下的WCA和SCA
Figure 9. (a) SAP’s WCA and SCA of the coating under the wear of 200 g weight and 25 μm sandpaper; (b) ASP’s WCA and SCA of the coating under the wear of 200 g weight and 25 μm sandpaper; (c) Schematic diagram of sand impinging test; (d) SAP’s WCA and SCA of coating under sand impinging
图 10 (a-c) SAP涂层的SEM图像; (d-f) SAP涂层的摩擦200次后的SEM图像
Figure 10. (a-c) SEM images of SAP coatings; (d-f) SEM images of SAP coatings after 200 abrasion times
图 11 磨损前后的原理图: (a) SiO2/ANFs-PDA涂层; (b) SiO2涂层
Figure 11. Schematic diagram of coating surface before and after abrasion: (a) Coating of SiO2/ANFs-PDA; (b) Coating of SiO2
图 12 SAP涂层在温差循环测试中的接触角
Figure 12. Contact angle of SAP coating in temperature difference test cycles
图 13 (a) SAP涂层在不同pH去离子下浸泡后的疏水角; (b) SAP涂层在去离子水中浸泡时出现的银镜效应
Figure 13. (a)Water contact angle of SAP coating after immersion at different pH deionized water; (b)Silver mirror effect of SAP coating during immersion in deionized water
图 14 SAP超疏水涂层的自清洁测试: (a)载玻片; (b) SAP涂层
Figure 14. Self-cleaning test of SAP superhydrophobic coating:(a) Glass slide; (b) SAP coating
图 15 电化学测试结果: (a)SAP 涂层的Nyquist 图; (b)原始铝片的Nyquist 图; (c)Tafel极化曲线
Figure 15. Electrochemical test results: (a)Nyquist diagram of SAP coating; (b)Nyquist diagram of aluminum sheet; (c)Tafel polarization curve
表 1 底层不同预固化时间对涂层疏水性能的影响
Table 1. The effect of different hardening times of the first layer on the hydrophobic properties of coatings
Hardening time/min 20 22 24 26 28 30 WCA/(º) 144 147 158 158 × × SCA/(º) 27 18 5 5 × × Notes: When the pre-curing time is greater than 26 minutes, the mechanical performance of the coating is poor, and the testing data becomes meaningless. 
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表 2 涂层附着力测试
Table 2. Coating adhesion test
Adhesion tesr times 0 1 4 7 Sample 
WCA 157° 157° 156° 153°
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