Preparation of myristic acid modified SiO2/hyperbranched-PDMS self-healing coating and its superhydrophobic performance
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摘要: 为了提高超疏水涂层的耐久性，通过设计“基底-黏性自修复聚合物-疏水粒子”自下而上的涂层体系，制备了具有自修复功能的超疏水表面：以含有丰富氢键的超支化聚硅氧烷(HB-PDMS)作为黏性自修复聚合物，通过十四酸(MA)对纳米SiO2进行疏水改性作为疏水粒子以构筑表面粗糙结构。探究了SiO2改性的最佳工艺：当MA与SiO2质量比为1∶1，改性时间为3 h时，所制备的超疏水涂层接触角为152.61°，滚动角为1.9°，具有优异的防污性能。涂层经受刀片划伤后通过简单热处理即可修复划痕，自修复性能优异。与纯铝相比，该复合涂层具有良好的防腐性能，缓蚀效率可达87.53%。此外，经历5次胶带剥离、磨损长度为30 cm的线性耐磨测试、50 min的超声振荡测试、10次温差循环和24 h紫外照射后，接触角依旧保持在150°以上，说明该涂层具有良好的耐候性和机械稳定性。该研究为自修复超疏水涂层的制备提供了新策略，有望应用于建筑防污领域。Abstract: In order to improve the durability of superhydrophobic coatings, in this work, we designed a bottom-up coating system of “substrate-viscous self-healing polymer-hydrophobic particle”, thereby the superhydrophobic surface with self-healing function was successfully fabricated: Hyperbranched polydimethylsiloxane (HB-PDMS) with abundant hydrogen bonds as viscous self-healing polymer; Nano-SiO2 was hydrophobic modified by myristic acid (MA) as hydrophobic particles to construct rough surface structure. When the mass ratio of MA to SiO2 is 1∶1 and the modification time is 3 h, the superhydrophobic coating prepared has a contact angle of 152.61° and a sliding angle of 1.9°, which has excellent antifouling performance. The coating can be healed by simple heat treatment after being scratched by the blade, and has excellent self-healing performance. Compared with pure aluminum, the composite coating has better anti-corrosion performance and the corrosion inhibition efficiency can reach 87.53%. In addition, After 5 tape peel tests, linear wear tests with a wear length of 30 cm, ultrasonic shock tests of 50 min, 10 temperature differential cycles and 24 h ultraviolet irradiation, the contact angle remained above 150°, indicating that the coating has good mechanical stability and weather resistance. This study provides a new effective strategy for the preparation of self-healing superhydrophobic coatings, which is expected to be applied in the field of building antifouling.
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Key words:
- self-healing /
- superhydrophobic /
- SiO2 /
- modification /
- myristic acid /
- building antifouling
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图 1 (a) 十四酸(MA)改性SiO2 (MA-SiO2)的反应机制；(b) MA-SiO2/超支化聚二甲基硅氧烷(HB-PDMS)涂层的制备过程示意图
Figure 1. (a) Diagram of the reaction mechanism of myristic acid (MA) modified SiO2 (MA-SiO2); (b) Schematic diagram of the preparation process of MA-SiO2/hyperbranched polydimethylsiloxane (HB-PDMS) coating
THF—Tetrahydrofuran
图 2 MA改性剂用量((a), (b)) 和改性时间 ((c), (d)) 对SiO2疏水度和涂层润湿性的影响
Figure 2. Effect of MA modifier dosage ((a), (b)) and modification time ((c), (d)) on hydrophobicity of SiO2 and wettability of coatings
m (MA)∶m (SiO2)—Mass ratio of myristic acid and SiO2
图 3 MA改性SiO2前 ((a1)~(a3), (c)) 和后 ((b1)~(b3), (d)) 的SEM图像与EDS图谱
Figure 3. SEM images and EDS mapping of SiO2 before ((a1)-(a3), (c)) and after ((b1)-(b3), (d)) MA modification
图 4 HB-PDMS涂层 ((a), (c)) 和MA-SiO2/HB-PDMS涂层 ((b), (d)) 的SEM图像与EDS图谱
Figure 4. SEM images and EDS mapping of HB-PDMS coating ((a), (c)) and MA-SiO2/HB-PDMS coating ((b), (d))
图 6 MA-SiO2/HB-PDMS复合涂层的损伤-修复过程显微照片 ((a)~(c), ((a1)~(c1)))；(d) MA-SiO2/HB-PDMS复合涂层的修复机制；(e) MA-SiO2/HB-PDMS涂层修复前后Tafel测试结果；(f) 从极化曲线获得的MA-SiO2/HB-PDMS涂层自修复测试前后的腐蚀参数；(g) MA-SiO2/HB-PDMS涂层防Cl−渗透机制示意图
Figure 6. Micrographs of damage-repair process of MA-SiO2/HB-PDMS composite coating ((a)-(c), ((a1)-(c1))); (d) Repair mechanism of MA-SiO2/HB-PDMS composite coating; (e) Tafel results before and after self-healing of MA-SiO2/HB-PDMS coatings; (f) Corrosion parameters obtained from potentiodynamic polarization curves with the self-healing tests of MA-SiO2/HB-PDMS coatings; (g) Schematic diagram of anti-Cl− penetration mechanism of MA-SiO2/HB-PDMS coatings
i—Current density; Ecorr—Corrosion potential; Icorr—Corrosion current density
图 7 (a) 裸铝和涂覆MA-SiO2/HB-PDMS涂层的铝的极化曲线；(b) Nyquist图；(c) Bode图；((d), (e)) 等效电路图
Figure 7. (a) Polarisation curves for bare Al and Al coated with MA-SiO2/HB-PDMS; (b) Nyquist plot; (c) Bode plot; ((d), (e)) Equivalent circuit diagram
Z'—Impedance real part; Z"—Impedance imaginary part; Rs—Solution resistance between the reference electrode and specimens; Rct—Charge transfer resistance; Rcoat—Resistance of the superhydrophobic coating; Cdl, Ccoat—Double layer capacitance on metal surface and capacitance on coating itself, respectively; W—Warburg resistance
图 8 纯玻璃(上)和MA-SiO2/HB-PDMS涂覆玻璃(下)的防污效果
Figure 8. Antifouling effect of pure glass (top) and MA-SiO2/HB-PDMS coated glass (bottom)
图 9 各涂层耐候性测试结果：(a) 温差循环实验；(b) 耐紫外老化实验
Figure 9. Results of weather resistance tests on coatings: (a) Temperature cycling test; (b) UV ageing test
图 10 各涂层的机械稳定性测试结果：((a), (b)) 线性耐磨试验；(c) 胶带剥离试验；(d) 超声振荡试验
Figure 10. Mechanical stability test results of the coating: ((a), (b)) Linear wear test; (c) Tape peel test; (d) Ultrasonic shock test
表 1 极化曲线中获得的裸铝和MA-SiO2/HB-PDMS涂层铝表面的腐蚀参数
Table 1. Corrosion parameters of bare Al and MA-SiO2/HB-PDMS coated Al surface obtained from polarization curves
Samples Ecorr (vs Ag/AgCl)/mV Icorr/(μA·cm−2) Bare Al −696 4.81 Al coated with MA-SiO2/HB-PDMS 166 0.60 
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