Preparation of superhydrophobic coating with self-similar structure by one-step menthod and application on concrete surface
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摘要: 探寻一种简单方法制备具有自修复性能的环氧树脂(EP)-硅酮胶-SiO2超疏水复合涂层，并且能够涂覆于类似于混凝土等结构物表面，该涂层在受到化学及机械破坏的情况下，可以实现自修复。通过简单的一步法在混凝土粗糙结构表面制备一种具有自修复性能的EP-硅酮胶-SiO2超疏水复合涂层，具体步骤为将EP、高分子中性硅酮胶和纳米SiO2等材料溶解于乙醇溶液，经8 h磁力搅拌和20 min超声分散后得到超疏水涂层溶液，采用喷涂法在混凝土表面成功制备具有自修复性能的多层相似结构超疏水涂层。当EP含量为2wt%，高分子中性硅酮胶含量为3wt%，纳米SiO2含量为3wt%时涂层疏水性能最佳，此时，接触角(CA)为156°±1.2°，滚动角(SA)为6°±0.8°。涂层在2.66 kPa的压强下可以经受8 m磨损(1.7 μm砂纸)，在盐性环境(2 mol/L NaCl溶液)、酸性环境(pH=3，醋酸)中腐蚀8 h仍保持超疏水性；可承受碱性破坏(pH=12，NaOH溶液)-自修复循环8次，机械破坏-自修复可循环4次；同时涂层展现出优异的自清洁及防水性能。力学及环境腐蚀破坏实验表明涂层的自相似结构可以保证上层被破坏后由下层(具有相同的微纳米粗糙结构)来保持超疏水性；损坏-修复实验表明涂层经过加热可以使高分子中性硅酮胶带动涂层内部低表面能分子及纳米SiO2发生迁移而实现涂层的修复。该涂层简单的制备方法、良好的耐机械磨损性及优异的自修复性，为超疏水涂层的实际应用提供了可能。Abstract: To explore a simple method to prepare a epoxy resin (EP)-silicone sealant-SiO2 superhydrophobic composite coating with self-repairing property and capable of being applied to the surface of a structure like concrete, which can be self-repairing in the case of chemical and mechanical damage, The EP-silicone sealant-SiO2 superhydrophobic composite coating with self-repairing property was prepared on the surface of concrete by one-step method. The specific steps were to dissolve the EP, silicone adhesive and nano-SiO2 in anhydrous ethanol solution, and the compound solution would be obtained after 8 h magnetic stirring and 20 min ultrasonic dispersion. Then the superhydrophobic coating with self-repairing performance would be successfully prepared on the surface of concrete by spraying compound solution. When the content of epoxy resin is 2wt%, the content of silicone adhesive is 3wt% and the content of nano-SiO2 is 3wt%, the coating could exhibit optimal superhydrophobic performance. The average contact angle (CA) of the coating is 156°±1.2° and the average slid angle (SA) is 6°±0.8°. After 8 m of abrasion length at a pressure of 2.66 kPa (Sandpaper: 1.7 µm) or 8 h of immerse time in saline (2 mol/L NaCl solution) or acidic environments (pH=3, acetic acid), the coating still maintain superhydrophobicity. The contact angle of the coating remains above 150° after 8 cycles of alkaline damage and self-repair (pH=12, NaOH solution) or 4 cycles of mechanical damage and self-repair. Moreover, the coating also displays excellent self-cleaning and waterproof performance according to the self-cleaning test and waterproof test. The experiments of mechanical and environmental corrosion damage show that the similar structure of the coating can ensure that the micro-nano rough structure of the lower layer maintain superhydrophobicity after the upper layer being damaged. The damage and self-repair experiments show that the coating can be repaired when the coating is heated. This is because the flow of silicone adhesive can promote the migration of low surface energy molecules and nano-SiO2 particles in the coating during the heating process. The simple preparation method, good mechanical wear resistance and excellent self-healing properties of this coating offer the possibility of practical application of superhydrophobic coatings.
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Key words:
- superhydrophobic /
- self-repair /
- composite coating /
- self-similarity /
- epoxy resin
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图 1 环氧树脂(EP)-硅酮胶-SiO2超疏水复合涂层制备流程图
Figure 1. Flow chart of epoxy resin (EP)-silicone sealant-SiO2 superhydrophobic composite coating preparation
图 2 EP-硅酮胶-SiO2超疏水复合涂层表面的不同放大尺寸图
Figure 2. Different enlarged dimensions of the EP-silicone sealant-SiO2 superhydrophobic composite coating surface
图 3 加热前后的EP-硅酮胶-SiO2超疏水复合涂层的SEM图像
Figure 3. SEM images of EP-silicone sealant-SiO2 superhydrophobic composite coating before and after heating
图 4 加热前后EP-硅酮胶-SiO2超疏水复合涂层的红外光谱
Figure 4. Infrared spectra of EP-silicone sealant-SiO2 superhydrophobic composite coating before and after heating
图 5 EP-硅酮胶-SiO2超疏水复合涂层混凝土试样的接触角(CA)和滚动角(SA)随磨损次数的变化
Figure 5. Variation of contact angle (CA) and slid angle (SA) with abrasion cycles for concrete specimens with EP-silicone sealant-SiO2 superhydrophobic composite coating
图 6 EP-硅酮胶-SiO2 超疏水复合涂层分别在盐溶液(NaCl) (a)、酸性溶液(乙酸，pH=3) (b) 和碱性溶液(NaOH，pH=12) (c) 作用下CA和SA变化曲线
Figure 6. CA and SA change curves under the action of salt solution (NaCl) (a), acidic solution (acetic acid, pH=3) (b) and alkaline solution (NaOH, pH=12) (c) of EP-silicone sealant-SiO2 superhydrophobic composite coating
图 7 EP-硅酮胶-SiO2 超疏水复合涂层碱损伤-加热修复的循环次数 (a)、碱性(pH=12)溶液破坏后的SEM图像 (b) 和加热恢复后的SEM图像 (c)
Figure 7. Number of cycles of alkali damage and heating repair (a), SEM image after damage by alkaline (pH=12) solution (b) and SEM image after heating recovery (c) of EP-silicone sealant-SiO2 superhydrophobic composite coating
图 8 EP-硅酮胶-SiO2超疏水复合涂层砂纸摩擦损伤修复涂层的循环次数 (a)、10 m砂纸摩擦破坏后的SEM图像 (b)、加热恢复后的SEM图像 (c)
Figure 8. Cycle times of sandpaper friction damage and repair (a), SEM image of 10 m abrasive paper after friction damage (b), and SEM image after heating recovery (c) of EP-silicone sealant-SiO2 superhydrophobic composite coating
图 9 EP-硅酮胶-SiO2超疏水复合涂层自修复机制
Figure 9. Self-repair mechanism of EP-silicone sealant-SiO2 superhydrophobic composite coating
图 10 ((a)~(d)) 涂有EP-硅酮胶-SiO2超疏水复合涂层混凝土自清洁照片及模拟图；((e)~(h)) 普通混凝土清洁照片及模拟图
Figure 10. ((a)-(d)) Self-cleaning photos and simulations of concrete coated with EP-silicone sealant-SiO2 superhydrophobic composite coating; ((e)-(h)) Cleaning photos and simulations of ordinary concrete
θ—Angle of slope
图 11 混凝土表面EP-硅酮胶-SiO2超疏水复合涂层的吸水率 (a) 和吸水速率 (b)
Figure 11. Plots of water absorption (a) and water absorption rate (b) of EP-silicone sealant-SiO2 superhydrophobic composite coating coated concrete
表 1 EP-硅酮胶-SiO2超疏水复合涂层各类材料含量
Table 1. Content of various materials of EP-silicone sealant-SiO2 superhydrophobic composite coating
Material Ethanol EP Neutral
silicone glueSiO2 Curing
agentContent/wt% 91.5 2 3 3 0.5 
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