Mechanically stable superhydrophobic surface fabricated by self-growth of ZnO nanoflowers on vulcanized silicone rubber
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摘要: 制造的复杂性和对机械接触的敏感性严重阻碍了超疏水材料在实际应用的发展。为在柔性基质(硫化的硅橡胶)表面制备机械耐久的柔性超疏水表面，利用硫化硅橡胶溶胀过程可逆的特性，改进溶胶-凝胶法，将硅橡胶片预先用正丁胺水溶液溶胀，然后浸入硝酸锌/乙醇溶液中。利用正丁胺水溶液和硝酸锌/乙醇溶液在硅橡胶表面的交互扩散、反应，使ZnO纳米花在橡胶表面原位生长。超疏水的粗糙结构的构筑来自于硝酸锌与正丁胺的协同作用，其静态接触角(CA)可达(158±1.5)°，滑动角(RA)可达(4.5±0.5)°。SEM图像显示，100~200 nm的ZnO纳米片生长在硅橡胶表面，ZnO纳米片“嵌入”到橡胶表面，而不是沉积在橡胶表面，因此提升了其机械耐久性。而通过向橡胶中添加硅烷偶联剂γ-氨丙基三乙氧基硅烷(KH550)，可进一步提升ZnO纳米片与橡胶基体界面相互作用，即使承受300次线性磨损，仍能保持超疏水特性，表现出优异机械稳定性。而且经过500次循环弯曲变形，其疏水性也几乎没有变化，解决了超疏水涂层在基体弯曲变形时的脱落问题。这种超疏水橡胶制备技术简单且适合工业生产，具有极高的实用前景。Abstract: The development of superhydrophobic materials in practical applications has been severely hindered by the complexity of manufacturing and the sensitivity to mechanical contact. In order to prepare a mechanically durable flexible super-hydrophobic surface on the surface of a flexible substrate (vulcanized silicone rubber), using the reversible characteristics of the swelling process of vulcanized silicone rubber and the improved sol-gel method, the silicone rubber sheet was swelled with a n-butylamine aqueous solution in advance, and then immersed in zinc nitrate/ethanol solution. Due to the cross-diffusion, contact and reaction between zinc nitrate and n-butylamine aqueous solution on the surface of silicone rubber, ZnO nanoflowers were grown in-situ on the rubber surface. The construction of the superhydrophobic rough structure came from the synergistic effect of zinc nitrate and n-butylamine, with static contact angle and rolling angle being (158±1.5)° and (4.5±0.5)° respectively. SEM images show that ZnO nanosheets of 100-200 nm in thickness are generated and the ZnO nanosheets are “embedded”, not just “deposited” on the rubber surface, which improves the mechanical durability. By adding a silane coupling agent γ-aminopropyltriethoxysilane (KH550) to the silicone rubber compounds, the interface interaction between the ZnO nanosheets and the rubber matrix is further improved. Even with 300 times of linear wear, it could still maintain superhydrophobic and exhibit excellent mechanical stability. Moreover, after 500 cycles of bending deformation, its hydrophobicity hardly changes, which solves the problem of superhydrophobic coating falling off when the substrate is bent and deformed. High mechanical stability and simple preparation process endow the superhydrophobic rubber a high application prospect.
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Key words:
- sol-gel method /
- ZnO nanoflower /
- self-growth /
- mechanical stability /
- silicone rubber
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图 1 超疏水硅橡胶(SR)的制备工艺
Figure 1. Fabrication processes of superhydrophobic surface silicone rubber (SR)
SA—Stearic acid
图 2 在不同的溶胶-凝胶反应时间和温度下的SR片的接触角(CA)：(a) 反应温度为60℃；(b) 反应时间为4 h
Figure 2. SR sheets contact angles (CA) at different sol-gel reaction time and temperature: (a) Reaction temperature of 60℃; (b) Reaction time of 4 h
图 3 不同溶胶-凝胶温度时超疏水SR表面形貌的SEM图像
Figure 3. SEM images of superhydrophobic SR surface morphologies at different sol-gel temperatures
图 4 不同放大倍率下最佳配比的超疏水SR的横截面SEM图像
Figure 4. SEM images of cross-sections of superhydrophobic SR with optimal ratio at different magnifications
图 5 40℃下溶胶-凝胶反应的超疏水SR超声处理前后的SEM图像
Figure 5. SEM images of superhydrophobic SR of the sol-gel reaction at 40℃ before and after ultrasonic treatment
图 6 最佳配比超疏水SR超声处理前后的SEM图像及接触角照片
Figure 6. SEM images and contact angle photos of superhydrophobic SR with the best ratio before and after ultrasonic treatment
图 7 未处理和处理过的超疏水SR表面上的水滴((a)、(b))、将处理过的膜浸入去离子水中 (c) 和在弯曲过程中处理过的表面上的水滴((d)~(g))照片
Figure 7. Photographs of superhydrophobic SR of water droplet on untreated and treated surface ((a), (b)), treated film was immersed in deionized water (c) and water droplets on the surface treated during the bending process ((d)-(g))
图 8 磨损测量示意图 (a)、不同磨损周期后的CA和滚动角(RA)值 (b) 和磨损后超疏水硅橡胶表面形态的SEM图像 ((c)、(d))
Figure 8. Schematic diagram of abrasion measurement (a), CA and roll-off angle (RA) values after different abrasion cycles (b) andSEM images of the superhydrophobic rubber surface morphology after abrasion ((c), (d))
图 9 Si-69填充基体和KH550填充基体在不同的磨损循环后的超疏水SR的CA和RA值 ((a)、(b))、Si-69填充基体的300次磨损循环后的超疏水SR的表面形态的SEM图像 ((c)、(e)) 和KH550填充基体在700次磨损循环后超疏水SR的表面形态的SEM图像 ((d)、(f))
Figure 9. CA and RA values of superhydrophobic SR of Si-69 filled matrix and KH550 filled matrix after different wear cycles ((a), (b)), SEM images of the superhydrophobic SR surface morphology of the Si-69 filled matrix after 300 cycles of abrasion ((c), (e)) and SEM images of the superhydrophobic SR surface morphology of the KH550 filled matrix after 700 cycles of abrasion ((d), (f))
图 10 磨损之前 (a) 和700个磨损周期后的 (b) 超疏水SR的EDS图谱
Figure 10. EDS spectra of superhydrophobic SR before abrasion (a) and after 700 cycles of abrasion (b)
图 11 磨损前超疏水试样的FTIR图谱
Figure 11. FTIR spectra of superhydrophobic samples before abrasion
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