Preparation and Anti-icing Performance of a Photothermal Self-Healing Superhydrophobic Membrane
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摘要: 针对柔性超疏水膜基材料在户外防冰应用中面临动态抗润湿能力、机械耐久性和因紫外线氧化引起的化学耐久性不足等问题。本文通过对石墨烯、TiO2和SiO2等纳米颗粒氟化修饰，并将修饰后的颗粒分布在热塑性聚氨酯(TPU)基质内，通过优化激光加工参数，制备了一种可大变形的光热自愈合超疏水膜(Photothermal self-healing superhydrophobic, PTHSHM)。本文研究了PTHSHM的动态抗润湿性、机械耐久性、防/除冰性能以及在物理/化学损伤下的愈合性能。PTHSHM在400%应变下，经1000次循环拉伸后表面水接触角不低于156.4°。同时，断裂后的PTHSHM在0.4 W/cm2红外光照射下8分钟后愈合效率达到97.6%。此外，在化学损伤-愈合方面，经过10次氧等离子刻蚀-修复循环后，其表面水接触角仍在(5±2)°和155°之间可逆转换。此外，在−15℃的环境下，PTHSHM表面延迟结冰时间为350 s，冰粘附强度低至55 kPa，20 μL冰滴在0.1 W/cm2的太阳光下的融化并滚落时间为77 s。综上，PTHSHM表现出良好的机械和化学耐久性，在延迟结冰时间和降低冻结粘附方面优势显著。Abstract: To address challenges related to dynamic anti-wetting, mechanical durability, and chemical resistance due to UV oxidation faced by flexible superhydrophobic membrane materials in outdoor anti-icing applications, this paper presents a study on the fabrication and performance of a photothermal self-healing superhydrophobic membrane (PTHSHM). The membrane was prepared by fluorinated-graphene/TiO2/ SiO2 nanoparticles and dispersing them in a thermoplastic polyurethane (TPU) matrix, followed by optimizing laser processing parameters to achieve the hydrophobic modification. The PTHSHM exhibited impressive performance in terms of dynamic anti-wetting, maintaining a water contact angle of 156.4° even after 1000 cycles of stretching with a 400% strain. Moreover, it demonstrated efficient self-healing abilities, achieving a healing efficiency of 97.6% in 8 minutes under 0.4 W/cm−2 infrared illumination. Moreover, the membrane showed strong resistance to chemical damage, retaining a water contact angle of at least 155° after 10 cycles of oxygen plasma etching and repair. In anti-icing tests, the delayed freezing time and ice adhesion strength of PTHSHM is measured as 350 s and 55 kPa. A 20 μL ice droplet melted and rolled off in 77 s under 0.1 W/cm2 sunlight. Overall, the PTHSHM displays excellent mechanical and chemical durability, along with significant advantages in delaying ice formation and facilitating ice removal, making it a promising candidate for various outdoor anti-icing applications.
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Key words:
- superhydrophobic /
- fluorinated graphene /
- high strain /
- self-healing /
- photo-thermal de-icing /
- Self-cleaning
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图 1 光热自愈合超疏水膜(PTHSHM)制备流程示意图。其中，① 、②分别为TiO2/SiO2纳米粒子和石墨烯改性过程，③为复合薄膜(FM)预聚物制膜过程，④为激光加工过程
Figure 1. Schematic diagram of the photothermal self-healing superhydrophobic (PTHSHM) fabrication process. Here, ① and ② represent the TiO2/SiO2 nanoparticle and graphene modification processes, respectively, ③ is the pre-polymer film (FM) formation process, and ④ is the laser irradiation process
图 2 (a)PTHSHM的SEM图，插图为对应的接触角图像；(b)在倾斜1°的PTHSHM表面上表征WSA(c)纯热塑性聚氨酯(TPU)、FM、PTHSHM的FTIR光谱；(d) FM和PTHSHM表面化学元素的EDS能谱分析
Figure 2. (a) SEM images of PTHSHM, with insets showing the corresponding contact angle images; (b) Characterization of WSA on the PTHSHM surface at a 1° tilt angle; (c) FTIR spectra of pure thermoplastic polyurethane (TPU), FM, and PTHSHM; (d) EDS elemental analysis of the chemical composition on the surfaces of FM and PTHSHM
图 4 PTHSHM的10、100、200、500和1000次循环拉伸应力-应变曲线，插图分别是第10个循环和第1000个循环中的水接触角光学图像
Figure 4. The stress-strain curves of the PTHSHM after 10, 100, 200, 500, and 1000 stretching cycles, with insets showing the optical images of water contact angle during the 10 th and 1000 th cycles respectively
图 5 不同超疏水膜在循环拉伸下的润湿性比较
Figure 5. Comparison of the wetting properties of different superhydrophobic membranes under stretching cycles
图 6 PTHSHM在不同pH溶液中的接触角变化
Figure 6. Changes in Contact Angle of PTHSHM in Solutions with Different pH Values
图 7 PTHSHM磨损距离与接触角变化
Figure 7. Wear Distance and Corresponding Contact Angle Changes of PTHSHM
图 8 PTHSHM在400%应变下的自清洁测试
Figure 8. Schematic illustration and process of self-cleaning of PTHSHM at 400% strain
图 9 (a)PTHSHM光热性能，(b)、(c)PTHSHM的断裂损伤和愈合过程及相应的SEM图，(b)中插图为局部放大图，(c1)(c2)插图为对应的接触角图像，(c3)为(c2)修复位置的高分辨图；(d)自修复机制图
Figure 9. (a) Photothermal Performance of PTHSHM, (b), (c) Fracture damage and healing process of PTHSHM and corresponding SEM images, with the inset in (b) being a zoomed-in view, the insets in (c1) and (c2) showing the corresponding contact angle images, and (c3) being a magnified view of the repaired area in (c2); (d) Self-healing mechanism image
图 10 PTHSHM经0.4 W/cm2的红外辐照8分钟条件下的5个愈合周期中的愈合效率曲线
Figure 10. The healing efficiency curves of the PTHSHM during the 5 cycles of healing process that was carried out under the 0.4 W/cm2 IR irradiation for 8 min
图 11 自修复效率与愈合时间的文献研究对比
Figure 11. Comparative literature study on self-healing efficiency and healing time
图 12 O2等离子体刻蚀-加热循环的水接触角，插图为对应的水接触角图像
Figure 12. Water contact angles during O2 plasma etching- healing cycles, with insets showing the corresponding water contact angle images
图 13 PTHSHM在-10℃和-16.5℃下的光热效应曲线
Figure 13. Photothermal effect curves of PTHSHM at -10°C and -16.5°C
图 14 (a)铝、玻璃、I-PSHM、D-PSHM、H-PSHM表面的延迟结冰过程；(b)铝、玻璃、I-PSHM、D-PSHM、H-PSHM表面在-16.5℃下的冰粘附强度；(c)PTHSHM和铝的光热除冰性能比较
Figure 14. (a) Delayed icing process on the surface of aluminum, glass, I-PSHM, D-PSHM, and H-PSHM; (b) ice adhesion strength on the surfaces of aluminum, glass, I-PSHM, D-PSHM, and H-PSHM at -16.5°C; (c) comparison of the photothermal de-icing performance between PTHSHM and aluminum
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