具有纳米防污剂协同作用和自修复功能的仿生超疏水涂层的制备及防污机理研究

Adhesion and corrosion of marine organisms on marine materials has become a global problem influencing the performances of marine facilities serving seriously. The study of long-term stable biomimetic superhydrophobic coating is an important and promising method for the development of green antifouling coatings. However, weak adhesive force, poor damage property and low antifouling property limit the application of biomimetic superhydrophobic coating. Therefore, in this paper, a green biomimetic superhydrophobic antifouling coating with a nano-antifouling agent and self-healing property is prepared in detail. The matrix resin with low surface energy and adhesive force was synthesized by using Si- and F-modified two-component polymer as the film-forming material. Nano-silver acted as the antifouling agent with no or low toxicity was grafted on the matrix resin through mercaptan coordination effect and in-situ polymerization. Then a multi-scale coarse structure was built on the matrix resin by using micro and nano hollow mesoporous silica with hydrophobic property and self-healing property as the building block to achieve long-term stable performance, high antifouling property and super-hydrophobicity of the coating. The effect of processing technological parameters of preparation on fouling performance of coating, the mechanism of antifouling synergistic effect between nano-antifouling agent and self-healing bionic coatings, the interfacial reaction between marine fouling organisms glia and coating and the common regularity of marine fouling prevention are the focused researches, which are the technical basis for the development of new environmentally friendly marine antifouling coating.

海洋生物对涉海材料的附着与腐蚀已成为严重影响海工装备服役性能的全球性问题。研究长效稳定的超疏水仿生涂层是当今绿色防污涂层发展的重点方向之一。但附着力低、不耐损伤以及防污效果有限是阻碍该类涂层实际应用的核心问题。为此，本项目拟制备一种具有纳米防污剂和自修复功能的超疏水绿色仿生防污涂层。该涂层以硅/氟改性双组分聚合物为成膜物，合成兼具低表面能和高附着力的基体树脂；以纳米银为防污剂，通过硫醇配位和原位聚合，将纳米银接枝到基体树脂中，并结合负载疏水材料的可自修复微/纳米中空介孔二氧化硅为涂层构筑单元，在低表面能基体树脂上构筑多尺度粗糙结构，实现涂层的超疏水性、耐持久性和高效防污性。重点研究各制备工艺参数对涂层防污性能的影响，探索纳米防污剂的释放控制与仿生自修复的协同防污效应机制，阐明海洋污损生物胶质与涂层之间的界面反应，揭示海洋生物污损防护的共性规律，为开发新型环境友好的海洋防污涂层奠定科学基础。

在海洋环境中，海洋生物对海洋结构钢的附着与腐蚀已成为严重影响海洋船舶和海工装备服役性能的全球性问题。在众多研究领域中，超疏水低表面能涂层是目前最有潜力的技术之一。然而，目前常规的疏水涂层不仅长效性和抑菌性差，而且与金属基体的附着力低，极大阻碍了疏水涂层在海洋领域的应用和推广。本项目从研究海洋污损生物附着机制入手，在改性的低表面基体树脂上，原位聚合纳米防污剂，并构筑纳米多尺度结构，研制了一种仿生纳米防污涂层，通过实海挂片，在海洋工程常用结构钢DH32试样表面提取了两种海洋优势菌种，经鉴定分别为革兰氏阴性菌需钠弧菌和革兰氏阳性菌芽孢杆菌，并以需钠弧菌为主要实验菌种，对海洋工程常用结构钢的微生物附着腐蚀行为与防护技术进行了较为系统的研究。研究表明，微生物的附着和微生物膜的形成能影响DH32试样的腐蚀行为，加快DH32试样的腐蚀速度。试样的腐蚀速度与微生物新陈代谢活性有关，活性越大，材料腐蚀越快。与此同时，本项目制备了一种耐微生物附着涂层，该涂层以有机硅改性丙烯酸为成膜物，以两种不同结构的载银纳米复合材料为杀菌剂。经试验发现，该涂层具有良好的水解性，杀菌剂释放平稳，能有效抑制微生物在试样表面的附着，减缓微生物对材料腐蚀的影响，其防护机制在于，一方面通过有机硅改性丙烯酸，使得涂层基料兼有自抛光和低表面能双重特点，另一方面以两种不同结构纳米银复合材料作为杀菌剂，通过纳米银的纳米效应和银离子释放进一步抑制了细菌的附着。