Page 43 - 摩擦学学报2025年第8期

第 8 期 孟维晟, 等: 遥爪型全氟聚醚自组装膜的表面性能及抗磨损和抗腐蚀性能研究 1141

multifunctional composite coatings that possessed anti-fouling, wear-resistant, and corrosion-resistant properties.
Polysiloxane and its modified materials primarily consist of silicone polymers or silicone-modified polymers as film
material coatings. These materials exhibited exceptional thermal stability, weather resistance, chemical corrosion
resistance, hydrophobicity, low surface energy, and excellent biocompatibility due to their unique valence bond
structure. However, this structure also affected their wear resistance and oleophobic properties. Consequently,
introducing both wear-resistant groups and amphiphobicity into organosilanes becomes necessary. In order to further
enhance the antifouling capabilities as well as the wear- and corrosion-resistance of coating materials, In this study,
amphiphilic Z-type telechelicperfluoropolyethers with double-terminated siloxanyl groups (PFSi, M n ≈10 000) were
synthesized through a substitution reaction using potassium borohydride and trimethoxy-chlorosilane. The silicon and
copper sheets were hydroxylated after cleaned and UV-Ozone treated, allowing for the growth of PFSi on their surfaces
to form self-assembled films. The surface properties and wear resistance of the self-assembled film were investigated,
along with the corrosion resistance of the remote claw type perfluoropolyether film. Results demonstrated that compared
to pure silicon wafers, the PFSi self-assembled film significantly improved water repellency, diiodomethane repellency,
seawater repellency, ethanol repellency and nonane repellency. Surface tension measurements using Owens two-liquid
method revealed that the surface tension of PFSi self-assembled films at different concentrations was less than 10 mN/m.
Scanning electron microscopy analysis showed that the self-assembled film on silicon wafer surfaces had a multi-layer
structure with thickness increasing as concentration increases. Furthermore, accelerated wear tests indicated excellent
wear resistance of the PFSi self-assembled film, which improved with higher concentration levels. Electrochemical
corrosion tests also demonstrated effective prevention of corrosion factors on copper substrates by the PFSi self-
assembled film thereby enhancing metal surface corrosion resistance. This study investigated the behavior of
amphiphilic telechelicpolymers in solid surface self-assembly to develop low surface energy films with abrasion and
corrosion resistance capabilities, thus providing a new approach for designing fluoropolymers with controllable self-
assembly functions.
Key words: perfluoropolyethers; siloxane; telechelicpolymers; multi-layer structure; self-assemble

近年来，随着工业化和城市化进程的不断加快， 现出高韧性 [22-23] . 得益于此，全氟聚醚在电子电气、汽车、
各类设备的表面经常暴露在各种恶劣环境和污染源 纺织、航天工程和生命工程等诸多领域都有广泛应
中，使得对材料表面的防污和耐蚀性需求日渐高涨. 用. 例如，将端基为酰氟基的全氟聚醚衍生物通过自
伴随需求和环境的日益复杂性，传统的保护型涂层材 组装的方式接枝于羟基化的玻璃表面，高浓度下其自
料逐渐显现出不足，因此制备具有防污耐磨耐腐蚀的 组装膜在展现出疏水性能的同时，还表现出优异的摩
多功能复合涂层具有重要的意义 [1-9] . 聚硅氧烷材料作 擦学性能和较高的耐磨寿命 [24] . 遥爪型聚合物作为
为1种以有机硅聚合物或有机硅改性聚合物为主的膜 1类通过中心聚合物链将两端基团或嵌段连接起来的
物质涂层材料，近年来在性能改进及应用方面得到了 聚合物，通常在选择性溶剂中表现出独特的自组装性
迅速发展 . 有机硅烷通过水解能够形成高度交联的 质，在大多数情况下各嵌段部分都处于高度不对称的
[10]
硬质网络，形成的聚硅烷涂层材料基于Si-O-Si价键结 状态，同时较短的嵌段主要位于聚合物链的外侧，这
构使其具有优异的热稳定性、耐候性、耐化学腐蚀 有利于分子间缔合从而形成交联 [25-29] . 遥爪型聚合物
性、耐磨性、疏水性、低表面能及优异的生物相容性 这种主链两端功能化的结构可以保持聚合物主链结
等特点 [11-15] ，但其特殊价键结构也使该材料存在强度 构独特的物理性质，同时其链端基团具有的交联特
低和与基材粘结性差等缺点. 通过将长烷基链、环氧 性，使其成为制备高弹性、高自愈性和高透明性膜的
[15]
化物、聚酯和聚氨酯等基团引入有机硅氧烷 ，能够 复合材料 [30-34] .
有效提高聚硅氧烷材料的强度和对基材的粘结性. 但 结合遥爪型聚合物的自组装行为、全氟聚醚自身
该方法使涂层的耐磨性和疏油性有所降低 [16-17] ，因此 的特殊性质以及硅氧烷在固体表面形成膜结构 [35-37] 的
需要将兼具耐磨性和双疏性的基团引入有机硅烷中， 特点，推断将硅氧烷作为遥爪型聚合物的疏溶剂端
以进一步提高涂层材料的防污耐磨耐蚀性能. 基，必然会导致其在含氟溶剂中的疏溶剂作用进一步
全氟聚醚(PFPE)作为1种高性能润滑剂，一方面 增强，而这可能使该类遥爪型聚合物在固体表面形成
能够通过含氟重复单元表现出低表面能、高热稳定性 独特的结构.
和化学惰性等特点 [18-21] ，另一方面在醚键的存在下表 因此，本文中设计并合成了由硅氧烷基构成全氟