聚酰亚胺基超疏水涂层的制备及其润湿性能研究
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摘要
超疏水性表面是指与水的接触角大于150°、滚落角小于10o的表面,由于它具有许多独特的表面性能,在防水、防雾、防雪、防腐蚀和自清洁等领域具有潜在的应用价值。但由于现有超疏水技术大多工艺复杂、无法大面积制备超疏水表面,同时所制备的超疏水表面的机械性能较差,极大地制约了超疏水表面在实际生产中的广泛应用。开发低成本、易实现规模化应用、并能提高机械性能的超疏水表面制备技术受到了越来越多的关注。
本文开发了两种聚酰亚胺基超疏水涂层的制备工艺并对其表面润湿性能进行了研究:
(1)利用聚酰胺酸涂料作为涂层基底材料,通过银离子交换和热处理技术在基底涂层表面构筑了具有孔洞状结构的纳米银层,在用低表面能的含氟癸基硫醇进行疏水改性后,获得了纳米银修饰的聚酰亚胺超疏水涂层。该超疏水涂层的表面粗糙度和静态接触角均随着热处理温度的升高而增大,而滚落角随着热处理温度的升高而减小;涂层表面的疏水性能随着离子交换溶剂极性和AgNO_3溶液浓度的增大而提高;同时涂层的疏水性也随离子交换时间延长而提高。该制备工艺的优化条件为:热处理温度大于350oC ;最佳离子交换用溶剂为水;优化离子子交换用AgNO_3浓度为0.1M;优化离子交换时间为2小时。
将纳米银修饰聚酰亚胺超疏水表面涂层应用在空调散热铝板表面,研究了超疏水表面的防结霜性能。结果表明,超疏水表面改性能显著延缓霜层在铝板表面的生长;防结霜性能随着表面疏水性能的增强而提高;霜层在普通铝板和疏水铝板表面上具有不同的生长过程和化霜过程。模拟能耗计算表明,用超疏水改性散热铝板表面能显著降低空调在制热时的能耗,提高空调的工作效率,在设计环保节能空调领域具有较好的应用前景。
(2)利用商业化的疏水SiO_2纳米粒子和聚酰胺酸涂料一步共混制备聚酰亚胺/SiO_2复合超疏水涂层。涂层的疏水性随着疏水SiO_2纳米粒子含量的增加而增强;当纳米粒子质量含量超过32.5%时,涂层表面接触角大于154o、滚落角小于6o。制备的超疏水表面具有良好的耐溶剂性能、耐刮伤性能和自清洁性能.该工艺的工艺过程简单、易实现规模化生产。
Superhydrophobic surfaces have very high water contact angles (CAs), particularly higher than 150°, and low water sliding angles (SAs) (less than 10o) . Because of theris special surface properties, these surfaces can be potentially applied in various fields such as water-proof materials, anti-fogging windows, anti-corrosion and self-cleaning coatings. However, technical problems such as complex fabricating processes, small areas and poor mechanical properties of the abtained superhydrophobic surfaces, have made these surfaces difficult to be applied. Therefore, new fabricating technologies aiming to reduce the cost, easily to be industrialized, and to improve mechanical properties of superhydrophobic surfaces, have attracted much attention.
This dissertation concentrated on developing two fabrication technologies of polyimide-based superhydrophobic coatings, and their wettabilities were systematically studied.
(1) Silver nano-particles were generated on polyamic acid film by ion exchange reaction with silver ion and subsequent thermal treatment. After modified with 1H,1H,2H,2H-perfluoro-1-decanethiol, superhydrophobic properties were obtained. Both of surface roughness and CAs of the superhydrophobic surface coating increased as the temperature of thermal treament increased, while SAs of the coatings decreased. Increasing the polarity of solvents, the concentration of AgNO_3 solution and the ion-exchange time can enhance the hydrophobicity of the surface coatings. We found the optimized conditions to achieve the superhydrophobic surface coatings as follows: the thermal treatment temperature should be over 350oC, the solvent for ion-exchange should be water, the concentration of AgNO_3 solution for ion-exchange should be larger than 0.1M, and ion-exchange time 2 hours. This method could be applied to fabricate superhydrophobic surfaces with large areas.
The anti-frosting property of superhydrophobic surfaces were investigated after the polyimide-based superhydrophobic surfaces with silver nano-particles coated on heat-exchanging aluminum (Al) plates. The results indicated the frosting growth process on superhydrophobically modified Al paltes could be greatly postponed compared with bare Al plates, and the anti-frosting property of modified Al plates was improved with the increase of hydrophobicity. The results also showed that frosting-processes and defrosting-processes on the superhydrophobically modified Al plates are quite different from those on bare Al plates. Simulated calculation of energy consumption during frosting-defrosting cycles confirmed that superhydrophobic coatings could save the energy consumed during heating process and improve the efficiency of air-conditioner. Therefore, they can be potentially used to save energy consumption in air-conditioner.
(2) Polyimide/SiO_2 composite superhydrophobic coatings were prepared by simply blend polyamic acid solution with commercial hydrophobic SiO_2 nano-particles. The hydrophobicity of the coatings was improved with the increase of weight ratio of hydrophobic SiO_2 nano-particles in the mixed coatings. Superhydrophobic surfaces with CA higher than 154o and SA lower than 6o were prepared when more than 32.5% wt of hydrophobic SiO_2 nano-particles were added. The as-prepared coatings showed good solvent durabilitiy, good abrasion resistance, as well as perfect self-cleaning property. The fabricating process is very simple and convenient for industrialization.
本文开发了两种聚酰亚胺基超疏水涂层的制备工艺并对其表面润湿性能进行了研究:
(1)利用聚酰胺酸涂料作为涂层基底材料,通过银离子交换和热处理技术在基底涂层表面构筑了具有孔洞状结构的纳米银层,在用低表面能的含氟癸基硫醇进行疏水改性后,获得了纳米银修饰的聚酰亚胺超疏水涂层。该超疏水涂层的表面粗糙度和静态接触角均随着热处理温度的升高而增大,而滚落角随着热处理温度的升高而减小;涂层表面的疏水性能随着离子交换溶剂极性和AgNO_3溶液浓度的增大而提高;同时涂层的疏水性也随离子交换时间延长而提高。该制备工艺的优化条件为:热处理温度大于350oC ;最佳离子交换用溶剂为水;优化离子子交换用AgNO_3浓度为0.1M;优化离子交换时间为2小时。
将纳米银修饰聚酰亚胺超疏水表面涂层应用在空调散热铝板表面,研究了超疏水表面的防结霜性能。结果表明,超疏水表面改性能显著延缓霜层在铝板表面的生长;防结霜性能随着表面疏水性能的增强而提高;霜层在普通铝板和疏水铝板表面上具有不同的生长过程和化霜过程。模拟能耗计算表明,用超疏水改性散热铝板表面能显著降低空调在制热时的能耗,提高空调的工作效率,在设计环保节能空调领域具有较好的应用前景。
(2)利用商业化的疏水SiO_2纳米粒子和聚酰胺酸涂料一步共混制备聚酰亚胺/SiO_2复合超疏水涂层。涂层的疏水性随着疏水SiO_2纳米粒子含量的增加而增强;当纳米粒子质量含量超过32.5%时,涂层表面接触角大于154o、滚落角小于6o。制备的超疏水表面具有良好的耐溶剂性能、耐刮伤性能和自清洁性能.该工艺的工艺过程简单、易实现规模化生产。
Superhydrophobic surfaces have very high water contact angles (CAs), particularly higher than 150°, and low water sliding angles (SAs) (less than 10o) . Because of theris special surface properties, these surfaces can be potentially applied in various fields such as water-proof materials, anti-fogging windows, anti-corrosion and self-cleaning coatings. However, technical problems such as complex fabricating processes, small areas and poor mechanical properties of the abtained superhydrophobic surfaces, have made these surfaces difficult to be applied. Therefore, new fabricating technologies aiming to reduce the cost, easily to be industrialized, and to improve mechanical properties of superhydrophobic surfaces, have attracted much attention.
This dissertation concentrated on developing two fabrication technologies of polyimide-based superhydrophobic coatings, and their wettabilities were systematically studied.
(1) Silver nano-particles were generated on polyamic acid film by ion exchange reaction with silver ion and subsequent thermal treatment. After modified with 1H,1H,2H,2H-perfluoro-1-decanethiol, superhydrophobic properties were obtained. Both of surface roughness and CAs of the superhydrophobic surface coating increased as the temperature of thermal treament increased, while SAs of the coatings decreased. Increasing the polarity of solvents, the concentration of AgNO_3 solution and the ion-exchange time can enhance the hydrophobicity of the surface coatings. We found the optimized conditions to achieve the superhydrophobic surface coatings as follows: the thermal treatment temperature should be over 350oC, the solvent for ion-exchange should be water, the concentration of AgNO_3 solution for ion-exchange should be larger than 0.1M, and ion-exchange time 2 hours. This method could be applied to fabricate superhydrophobic surfaces with large areas.
The anti-frosting property of superhydrophobic surfaces were investigated after the polyimide-based superhydrophobic surfaces with silver nano-particles coated on heat-exchanging aluminum (Al) plates. The results indicated the frosting growth process on superhydrophobically modified Al paltes could be greatly postponed compared with bare Al plates, and the anti-frosting property of modified Al plates was improved with the increase of hydrophobicity. The results also showed that frosting-processes and defrosting-processes on the superhydrophobically modified Al plates are quite different from those on bare Al plates. Simulated calculation of energy consumption during frosting-defrosting cycles confirmed that superhydrophobic coatings could save the energy consumed during heating process and improve the efficiency of air-conditioner. Therefore, they can be potentially used to save energy consumption in air-conditioner.
(2) Polyimide/SiO_2 composite superhydrophobic coatings were prepared by simply blend polyamic acid solution with commercial hydrophobic SiO_2 nano-particles. The hydrophobicity of the coatings was improved with the increase of weight ratio of hydrophobic SiO_2 nano-particles in the mixed coatings. Superhydrophobic surfaces with CA higher than 154o and SA lower than 6o were prepared when more than 32.5% wt of hydrophobic SiO_2 nano-particles were added. The as-prepared coatings showed good solvent durabilitiy, good abrasion resistance, as well as perfect self-cleaning property. The fabricating process is very simple and convenient for industrialization.
引文
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[1] Lafuma A.., Quere D., Superhydrophobic states, Nat. Mater., 2003, 2, 457-460
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