【作者】 刘旭东；

【导师】 冉千平；

【作者基本信息】 东南大学 ， 材料科学与工程， 2025， 博士

【摘要】 近年来,全球频繁遭受强冷空气寒潮袭击,冰冻灾害严重,对道路交通、航空航天和电力系统等基础设施的安全稳定运行造成严重威胁。然而,传统抗冰除冰技术依赖人为干预,且存在效率低、能耗大和危险性高等缺陷,构筑高效、高耐久的抗冰除冰材料已成目前行业研究热点。因此,本论文基于半导体和碳基材料的光致热原理,设计合成多种形貌的微纳米颗粒及聚合物树脂,制备了三种兼具被动抗冰和主动除冰性能的光热超疏水涂层。本论文主要研究成果如下:（1）基于多巴胺氧化自聚合和Cu²⁺还原机制,实现片状纳米MoS₂表面原位生长Cu纳米颗粒,并接枝十八硫醇（18-SH）构筑仙人掌形微纳米颗粒（MPCS）,同时结合水溶性季铵盐型聚硅氧烷（PMATF）的分子设计,制备出一种高硬耐磨的光热超疏水涂层（PM-MPCS）。涂层接触角高达171.83°;氙灯照射下,PM-MPCS表面温度可升至86.9℃,光热转换效率为77.41%;水滴冻结时间显著延长至2572 s,冰粒完全融化时间为317 s;经过330次砂纸磨损和210次胶带剥离循环后,涂层仍能保持良好的疏水效果。（2）在PMATF的研究基础上,引入有利于界面增强的γ-缩水甘油醚氧丙基三甲氧基硅烷,合成了无氟水性聚硅氧烷（PMATE）;通过对具有空腔结构的碳纳米球表面改性,制备了绣球形微纳米颗粒（CPPS）。调控树脂基体与微纳米颗粒之间的界面作用和微观形貌制得光热超疏水涂层（PM-CPPS）,有效提升涂层的光热转换性能和除冰效率,氙灯照射下,涂层表面温度可升至101.9℃,光热转换效率高达83.24%;冰粒在其表面的融化时间缩短至93 s.（3）为进一步提升涂层光热转换性能,基于具有空腔结构和极窄禁带宽度的CNT设计了葡萄形微纳米颗粒（CPAS）,制备了光热超疏水涂层（P-CPAS）。涂层在CPAS添加量仅为20%时达到最佳疏水效果,“颗粒-颗粒”和“树脂-颗粒”之间双重界面作用的增强显著提升了涂层机械稳定性,经过260次胶带剥离后仍保持良好的疏水效果。氙灯照射下,P-CPAS表面温度高达109.2℃,光热转换效率提升至89.04%;冰粒融化时间进一步缩短至71 s,实现了光热超疏水涂层微纳米颗粒低掺量、高耐久和高光热转换效率的有效协同。（4）通过涂层物相组成、微观结构与抗冰除冰特性之间构效关系的研究,揭示了树脂分子结构和微纳米颗粒形貌与光热超疏水涂层综合性能的本质相关性。低表面能导致的高接触角有利于结冰时间的延长,PM-MPCS异相成核能垒为99.99×10^-2C J,结冰时间最长,高达2582 s;较窄的禁带宽度有利于光子跃迁从而释放热能,葡萄形CPAS的禁带宽度为1.21 eV,P-CPAS的光热转换能力显著提升,从而将冰粒融化时间缩短了3.5倍。本文研究成果不仅为构筑新型光热超疏水涂层提供技术支撑,也为设计开发高效耐久的抗冰除冰材料提供理论指导。更多还原

【Abstract】 In recent years,the world has frequently experienced severe cold air outbreaks and cold wave events,leading to significant freezing disasters that threaten the safe and stable operation of critical infrastructure such as road traffic,aerospace,and power systems.However,traditional anti-icing and de-icing technologies rely on human intervention and have inherent drawbacks,including low efficiency,high energy consumption,and safety risks.As a result,the development of efficient and durable anti-icing and de-icing materials has become a major research focus in the field.Therefore,this dissertation is based on the photothermal principle of semiconductors and carbon-based materials,and designs and synthesizes various morphologies of photothermal micro/nanoparticles and highly compatible polymer resins,leading to the preparation of three types of photothermal superhydrophobic coatings with both passive anti-icing and active de-icing properties.The main research findings of this dissertation are as follows:（1）Based on dopamine oxidation self-polymerization and Cu²⁺reduction mechanisms,Cu nanoparticles were in situ grown on the surface of sheet-like MoS₂,and grafted with octadecyl mercaptan（18-SH）to construct cactus-shaped micro/nanoparticles（MPCS）.By combining the molecular design of water-soluble quaternary ammonium salt-type polysiloxane（PMATF）,a highly hard and wear-resistant photothermal superhydrophobic coating（PM-MPCS）was synthesized.The coating exhibited a contact angle of up to 171.83°.Under xenon lamp irradiation,the surface temperature of PM-MPCS could rise to 86.9℃,with a photothermal conversion efficiency of 77.41%.The water droplet freezing time was significantly extended to2572 s,and the complete melting time of ice particles was 317 s.After 330 sandpaper abrasion cycles and 210 adhesive tape peeling cycles,the coating still maintained excellent hydrophobic performance.（2）Based on the research of PMATF,γ-glycidoxypropyl trimethoxysilane,which is beneficial for enhancing the interface,was introduced,and fluorine-free waterborne polysiloxane（PMATE）was synthesized.By modifying the surface of carbon nanospheres with a cavity structure,hydrangea-shaped micro/nanoparticles（CPPS）were prepared.By controlling the interface interaction and microstructure between the resin matrix and micro/nanoparticles,a photothermal superhydrophobic coating（PM-CPPS）was obtained,which effectively enhanced the photothermal conversion performance and de-icing efficiency of the coating.Under xenon lamp irradiation,the surface temperature of the coating could rise to 101.9℃,with a photothermal conversion efficiency of 83.24%.The ice particle melting time on its surface was shortened to 93 s.（3）To further improve the photothermal conversion performance of the coating,grape-shaped micro/nanoparticles（CPAS）based on carbon nanotubes（CNT）with a cavity structure and a very narrow bandgap were designed,and a photothermal superhydrophobic coating（P-CPAS）was prepared.P-CPAS achieved the best hydrophobic effect with only 20%CPAS content.The enhanced dual interfaces between"particle-particle"and"resin-particle"significantly improved the mechanical stability of the coating.After 260 adhesive tape peeling cycles,P-CPAS still maintained excellent hydrophobic performance.Under xenon lamp irradiation,the surface temperature of the coating reached 109.2℃,and the photothermal conversion efficiency increased to 89.04%.The ice particle melting time was further reduced to 71 s,realizing an effective synergy of low content,high durability,and high photothermal efficiency for the photothermal superhydrophobic coating micro/nanoparticles.（4）Through the study of the phase composition,microstructure,and anti-icing/de-icing characteristics of the coatings,the intrinsic correlation between the resin molecular structure,micro/nanoparticle morphology,and the comprehensive performance of the photothermal superhydrophobic coatings was revealed.The high contact angle caused by low surface energy contributed to the extension of the freezing time.The heterogeneous nucleation energy barrier of PM-MPCS was 99.99×10^-2C J,with the longest freezing time of up to 2582 s.A narrower bandgap was more conducive to photon transition,thus releasing thermal energy.The bandgap of grape-shaped CPAS was 1.21 eV,and the photothermal conversion capacity of P-CPAS was significantly enhanced,shortening the ice particle melting time by 3.5 times.The results of this study not only provide technical support for the design of the construction of photothermal superhydrophobic coatings,but also offer theoretical guidance for the design and development of efficient anti-icing and de-icing materials.更多还原