Preparation and properties of SiO2/attapulgite composite self-healing superhydrophobic coating
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摘要: 在过去的几十年中，超疏水表面由于其特殊的性能而受到极为广泛的关注，但是在室外应用中，受环境中各种因素的影响，大多数超疏水表面很轻易会失去其超疏水性。采用简单的两步浸涂法制备得到一种表面坚固的可修复超疏水涂层。以聚硅氧烷与无水乙醇混合制得涂层底层；中性硅酮玻璃胶、纳米SiO2、微米级凹凸棒土(ATP)粉末以及聚硅氧烷共混制得涂层面层。利用扫描电子显微镜(SEM)、接触角测量仪、傅里叶变换红外光谱仪(FTIR)对涂层的微观形貌、润湿性、分子结构进行表征。确定了中性硅酮玻璃胶的最佳用量，考察了涂层的耐磨性能、自清洁性能以及机械磨损与酸碱环境下的自修复性能。结果表明：中性硅酮玻璃胶添加量在质量分数为1wt%时涂层疏水能力最佳，水接触角达到153.5°±1.5°。在50 g砝码(1.03 kPa)下经过360 cm的机械磨损，涂层仍具备140°以上的水接触角。并且涂层在受到一定程度的机械磨损或是酸碱破坏后，都可以通过高温加热实现涂层超疏水性能的修复，此外涂层还具备一定的耐水稳定性以及优异的自清洁能力。Abstract: In the past few decades, superhydrophobic surfaces have received extensive attention due to their special properties. However, in outdoor applications, most superhydrophobic surfaces easily lose their superhydrophobicity due to various factors in the environment. A simple two-step dip-coating method is used to prepare a strong and repairable superhydrophobic coating. In the first step, the coating’s bottom layer was prepared by mixing polysiloxane with absolute ethanol. For the second step, neutral silicone glass glue was mixed with silicon dioxide nanoparticles, micron attapulgite powder (ATP) and polysiloxane to create the coating’s upper layer. Scanning electron microscopy (SEM), contact angle measuring instrument, and fourier-transform infrared spectroscopy (FTIR) were used to determine the microscopic morphology, wettability and molecular structure of the coating. Furthermore, the optimal amount of neutral silicone glass glue was specified while at the same time the coating’s self-healing ability was observed under mechanical abrasion and in an acid-based environment. The results show that the hydrophobicity of the coating reaches the optimum when the amount of neutral silicone glass glue is 1% and the water contact angle reaches 153.5°±1.5°. In this way, the coating is able to maintain a water contact angle of over 140° even when 360 cm of mechanical wear with a weight of 50 g (1.03 kPa) is placed on it. In addition, after the coating has endured a certain amount of mechanical abrasion and acid-base damage, the superhydrophobic properties of the coating can be repaired by high-temperature heating. The coating also provides a certain water resistance-stability and an excellent self-cleaning ability.
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Key words:
- superhydrophobic /
- self-cleaning /
- self-repairing /
- silicone glue /
- attapulgite /
- nano SiO2
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图 1 SiO2/凹凸棒土(ATP)超疏水涂层制备流程图: (a) 底层的制备；(b) SiO2/ATP超疏水溶液的制备；(c) 表层的制备
Figure 1. SiO2/attapulgite powder (ATP) superhydrophobic coating preparation process: (a) Preparation of the bottom layer; (b) Preparation of SiO2/ATP superhydrophobic solution; (c) Preparation of the surface layer
图 2 不同中性硅酮玻璃胶含量下SiO2/ATP涂层的SEM图像，5 μm放大倍数下中性硅酮玻璃胶的含量：(a1) 0wt%；(b1) 1wt%；(c1) 2wt%；1 μm放大倍数下中性硅酮玻璃胶的含量：(a2) 0wt%；(b2) 1wt%；(c2) 2wt%
Figure 2. SEM images of different neutral silicone glass glue contents of SiO2/ATP coating: Under 5 μm magnification: (a1) 0wt%; (b1) 1wt%; (c1) 2wt%; Under 1 μm magnification: (a2) 0wt%; (b2) 1wt%; (c2) 2wt%
图 3 SiO2/ATP超疏水涂层的自清洁效应
Figure 3. Self-cleaning effect of SiO2/ATP superhydrophobic coating
图 4 (a) SiO2/ATP超疏水涂层水接触角随磨损周期的变化规律；(b) 不同表层构造的涂层水接触角随磨损周期的变化规律
Figure 4. (a) Change of water contact angle of SiO2/ATP superhydrophobic coating with abrasion cycles; (b) Variation of water contact angle of different coatings with wear cycles:
1—SiO2; 2—SiO2 with attapulgite; 3—SiO2 with attapulgite and polysiloxane; 4—SiO2 with attapulgite, polysiloxane and silicone glue
图 5 (a) 机械磨损下SiO2/ATP超疏水涂层的自修复规律；(b) SiO2/ATP超疏水涂层的FTIR图谱：初始涂层I；磨损后涂层II；加热修复后涂层III
Figure 5. (a) Self-healing law of SiO2/ATP suphyderrophobic coating under mechanical abrasion; (b) FTIR spectra of SiO2/ATP superhydrophobic coating: Initial coating I; Coating after abrasion II; Coating after heating repair III
CA—Contact angle
图 6 (a) 酸性环境下SiO2/ATP超疏水涂层的修复规律；(b) 碱性环境下SiO2/ATP超疏水涂层的修复规律
Figure 6. (a) Repair law of SiO2/ATP superhydrophobic coating in an acidic environment; (b) The repair law of SiO2/ATP superhydrophobic coating in an alkaline environment
图 7 SiO2/ATP超疏水涂层自修复机制示意图
Figure 7. Schematic diagram of the self-healing mechanism of SiO2/ATP superhydrophobic coating
图 8 (a) 水中浸泡时间对SiO2/ATP超疏水涂层接触角与滑动角的影响；(b) 5%NaCl水溶液浸泡时间对SiO2/ATP超疏水涂层接触角与滑动角的影响
Figure 8. (a) Effect of immersion time in water on the contact angle and sliding angle of SiO2/ATP superhydrophobic coating; (b) Influence of 5%NaCl solution immersion time on the contact angle and sliding angle of SiO2/ATP superhydrophobic coating
表 1 不同质量分数中性硅酮胶对SiO2/ATP涂层水接触角的影响
Table 1. The influence of different mass fractions of neutral silicone glue on the water contact angle of SiO2/ATP coating
Silicone glue content 0wt% 0.5wt% 1wt% 1.5wt% 2wt%
Water drop photo
Contact angle/(°) 147.99±0.5 149.49±1.5 153.49±1.5 152.49±1.5 151.99±1.5 
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