Preparation of myristic acid modified SiO2/hyperbranched-PDMS self-healing coating and its superhydrophobic performance
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摘要:
目的 超疏水材料因其优异的拒水性，可广泛应用于自清洁、防腐蚀、防覆冰等领域。但实际应用中，受恶劣环境（如腐蚀、磨损等）或者长期存储的影响，超疏水涂层的损坏与失效是不可避免的。无论考虑到成本或材料的可持续利用，提高其使用寿命都是至关重要的。为了提高超疏水涂层的耐久性，在超疏水涂层的基础上引入自修复功能，当涂层受到损伤后经过简单处理即可恢复到原始的超疏水状态。通过“基底-粘性自修复聚合物-疏水粒子”自下而上的涂层体系有利于构筑具有良好附着力的超疏水涂层。纳米二氧化硅作为常用于构造表面粗糙结构的无机粒子，由于其亲水特性，使其难以在粘性自修复聚合物中均匀分散。为了提升纳米二氧化硅与自修复聚合物间的相容性，有必要对纳米二氧化硅进行疏水改性。 方法 针对上述问题，本文采用“基底-粘性自修复聚合物-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合物（HB-PDMS）作为粘性自修复聚合物，通过十四酸（MA）对纳米二氧化硅（SiO2）进行疏水改性作为疏水粒子以构筑表面粗糙结构。探究了改性条件对二氧化硅疏水度的影响。通过核磁共振波谱仪、凝胶渗透色谱和红外光谱鉴定MA- SiO2/超支化聚二甲基硅氧烷的化学结构，表征涂层表面的化学成分；通过扫描电镜观察涂层表面形貌并测试元素组成；采用接触角测量仪表征样品的表面润湿性；使用刀片在涂层表面制造划痕，划穿涂层但不划破基底，再进行热处理，使用光学显微镜观察涂层表面划痕修复过程；采用电化学工作站对样品进行动电位极化曲线和交流阻抗测试，评价涂层的防腐性能；通过温差循环试验和耐紫外线试验评价涂层的耐候性；通过砂纸磨损实验和胶带剥离测试评价超疏水涂层的力学性能。 结果 通过十四酸对SiO2疏水改性，当十四酸与二氧化硅质量比为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°，涂层具有优异的防污性能。EDS结果和红外光谱测试结果表明十四酸成功接枝在纳米二氧化硅上，且涂层表面改性纳米二氧化硅和超支化PDMS均匀分布，MA-SiO2/HB- PDMS复合涂层的成功制备。经过损伤表面的自修复过程观察和Tafel测试，涂层于80 ℃下热处理2 h即可修复划痕，具有优异的自修复性能。修复温度越高，所需的修复时间越短。Tafel及Nyquist测试结果表明，相较于纯铝，涂层在3.5.wt %盐溶液中腐蚀电位正移了0.862 V，腐蚀电流密度减小了近一个数量级，缓蚀效率可达87.53 %，Rct值增大了约6000倍，该涂层可显著提高基底的防腐性能。经历5次胶带剥离、磨损长度为30 cm的线性耐磨测试、50 min的超声震荡测试、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。 结论 综上所述，本论文所制备的MA-SiO2/超支化PDMS自修复涂层具有优异的疏水性、耐腐蚀、防污性、耐候性和机械稳定性能。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 polymers (HB-PDMS) with abundant hydrogen bonds as viscous self-healing polymer ; nano-Silica (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.-
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的反应机制图；(b)MA-SiO2/超支化PDMS(HB-PDMS)涂层的制备过程示意图
Figure 1. (a) Diagram of the reaction mechanism of Myristic (MA) modified SiO2; (b) Schematic diagram of the preparation process of MA-SiO2/HB-PDMS coating
图 2 (a-b)MA改性剂用量和(c-d)改性时间对SiO2疏水度和涂层润湿性的影响
Figure 2. (a-b) Effect of MA modifier dosage and (c-d) modification time on hydrophobicity of SiO2 and wettability of coatings
图 3 MA(a1-a3, c)改性SiO2前和(b1-b3, d)后的SEM照片与EDS结果
Figure 3. SEM photographs and EDS results of MA (a1-a3, c) before and (b1-b3, d) after modification of SiO2
图 4 (a, c)HB-PDMS涂层和(b, d)MA-SiO2/HB-PDMS涂层的SEM照片与EDS结果
Figure 4. SEM photographs and EDS results of (a, c) HB-PDMS coating and (b, d) MA-SiO2/HB-PDMS coating
图 6 MA-SiO2/HB-PDMS复合涂层的(a-c)损伤-修复过程显微照片；(d)修复机制图；(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 (a-c) damage - repair process; (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
图 7 裸铝涂覆MA-SiO2/HB-PDMS铝的(a)极化曲线；(b)Nyquist图；(c)Bode图和(d-e)等效电路图
Figure 7. (a) Polarisation curves for bare and coated MA-SiO2/HB-PDMS aluminum; (b) Nyquist plot; (c) Bode plot and (d-e) equivalent circuit diagram
Z'-Impedance real part; Z"-Impedance imaginary part; Rs-Solution resistance between the reference electrode and specimens; Rct-The 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)超声震荡试验
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 aluminum and MA-SiO2/HB-PDMS coated aluminum surface obtained from polarization curves
Samples Ecorr /(mV vs. Ag/AgCl) icorr /(μA·cm−2) Bare −696 4.81 MA-SiO2/HB-PDMS 166 0.60 Notes: Ecorr-Corrosion potential; Icorr-Corrosion current density. 
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