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铝基仿生超疏水界面的构筑及性能
张斌斌
学位类型博士
导师侯保荣院士
2017-05-10
学位授予单位中国科学院大学
学位授予地点北京
学位专业海洋腐蚀与防护
关键词仿生超疏水 海洋防腐防污 自清洁 稳定性
其他摘要    金属及其合金在海洋环境下面临严重的腐蚀与生物污损问题,这极大地限制了该类材料在船舶舰艇、机械制造、航空航天等领域的广泛应用。润湿性是固体材料表面的重要性质之一。近年来,通过向自然学习,仿生超疏水材料在自清洁、油水分离、流体减阻、防雾防冰、雾气收集等领域展现出潜在的应用前景,受到了国内外科研人员的广泛关注。基于表面独特的斥水特性,金属基超疏水表面为海洋防腐防污提供了一种可能。本文发展了两种高效制备超疏水表面的方法,即高压硬质阳极氧化法和脂肪酸一步电沉积法,成功设计和构筑了铝基仿生超疏水表面,同时还深入研究其自清洁、海洋防腐防污、化学稳定性、机械稳定性和热稳定性等方面的性能,并揭示了相应机制。主要研究内容和结果如下:
    发展了一种高压硬质阳极氧化法制备铝基仿生超疏水表面,首次制备得到了基于纳米线自聚集的类康乃馨超亲水和超疏水表面,完善和丰富了阳极氧化表面形貌演变模型,首次将表面形貌随阳极氧化时间的变化归纳为纳米管结构(小管径)-纳米管结构(大管径)-纳米线结构-类金字塔结构-类康乃馨结构。此外,电化学和生物附着实验结果显示,类康乃馨超疏水表面在海洋防腐和防生物附着方面展现出非常好的应用潜力。此外,该表面还展现出优异的热稳定性和自清洁性能,能够使具有更低表面张力的高温水滴在表面仍呈Cassie模型接触,为该类超疏水表面在高温环境下的服役提供了可能。
    发展了一种高效制备铝基仿生超疏水表面的脂肪酸一步电沉积法,该方法操作简便、制备快速、成本低廉、环境友好、基材广适性强,能够在电沉积过程中使表面同时获得类荷叶微纳多级结构和低表面能,相比传统方法具有明显的优势,是一种应用潜力巨大的制备手段。论文采用一步电沉积法分别完成了硬脂酸体系、棕榈酸体系和肉豆蔻酸体系的研究工作,分别得到了静态接触角为169.7°、167.4°和162.1°的超疏水表面。进一步性能测试发现,采用脂肪酸一步电沉积法制备的超疏水表面均展现出优异的海洋防腐、防污特性,同时还具有良好的化学稳定性、耐久性、机械稳定性和自清洁等性能,这极大地拓展了该类超疏水材料的应用领域。
    本论文的研究还揭示了仿生超疏水表面在海洋环境下的防腐防污机制,即超疏水表面典型的微纳多级结构的间隙可截留空气层,形成的“空气垫”能够大幅降低腐蚀介质与基体之间的接触面积,腐蚀液体在表面呈Cassie模型接触,极大地阻碍了由腐蚀介质渗透或扩散至基体材料而引发的腐蚀过程。此外,超疏水表面所具有的极低的表面能和黏附力,让海洋微生物很难在其表面附着,极大地抑制了生物污损的发生。本论文的研究工作证实了仿生超疏水表面可以为金属或合金材料面临的海洋腐蚀与生物污损问题提供了一种有效的解决方案,是一种非常有前景的防护技术。;     Marine environmental corrosion and biofouling are ubiquitous and detrimental problems of metals and alloys, restricting their widely applications in vessels, machinery manufacturing, aerospace etc. Wettability is one of the fundamental properties of solid surfaces. Recent years, learning from nature, bio-inspired superhydrophobic materials have become a burgeoning research area and arouse much attention result from their potential applications in self-cleaning, oil/water separation, drag reduction, anti-fog, anti-icing, fog-harvest and so on. With unique surface water-repellent property, superhydrophobic surfaces on metallic substrates provide a very intriguing possibility for anti-corrosion and anti-biofouling applications. In this thesis, we developed two efficient fabrication methods, viz, high-voltage hard anodisation and one-step fatty acid electrodeposition techniques, successfully designing and fabricating superhydrophobic surfaces on aluminum substrates. Meanwhile, we investigated the performance of self-cleaning, marine anti-corrosion and anti-biofouling, chemical stability, mechanical stability, thermal stability etc. in details and revealed the corresponding anti-corrosion and anti-biofouling mechanisms.
    We developed a high-voltage hard anodisation method to fabricate bio-inspired superhydrophobic surfaces on aluminum substrates. Self-congregated Dianthus caryophyllus-like superhydrophilic/superhydrophobic surfaces were produced, which has not been achieved and reported so far. The dynamic morphology evolution model was enriched, depicting the morphology changes versus anodisation time as nanotubes structure with small diameter, nanotubes structure with large diameter, nanowires, Pyramid-like structure and Dianthus caryophyllus-like structure. Moreover, the electrochemical and biological adhesion experimental results demonstrate that the fabricated Dianthus caryophyllus-like superhydrophobic surface exhibits potential applications in marine anti-corrosion and anti-biofouling. Self-cleaning and chemical stability tests suggest that the as-prepared superhydrophobic surfaces exhibit excellent thermal stability and self-cleaning ability. The water droplets with higher temperature and lower surface tension can still retain its Cassie contact upon the surface, improving the possibility of the fabricated superhydrophobic surface serving under high temperature environments
    We developed an efficient fatty-acid-based one-step electrodeposition technique to fabricate bio-inspired superhydrophobic surfaces on aluminum substrates. This is a simple, fast, low-cost, environmental friendly and versatile method, achieving lotus leaf-like micro-nano hierarchical structure and low surface energy simultaneously during the electrodeposition process. Compared with traditional methods, the one step electrodeposition technique has distinct superiority with great potential. In this thesis, we carried out the one step electrodeposition research work in three reaction systems, including stearic-acid-system, palmitic-acid-system and myristic-acid-system, obtaining superhydrophobic surfaces with static water contact angle of 169.7°, 167.4° and 162.1° respectively. Further property characterizations reveal that the superhydrophobic surfaces fabricated through one-step electrodeposition strategy exhibit excellent marine anti-corrosion and anti-biofouling performance. Simultaneously, these superhydrophobic surfaces possess good chemical stability, durability, mechanical stability, self-cleaning capability, etc. expanding the application areas of this kind of superhydrophobic surfaces.
    The research works in this thesis also reveal the anti-corrosion and anti-biofouling mechanisms of bio-inspired superhydrophobic surfaces. The typical micro-nano hierarchical structure of superhydrophobic surface can entrap large amount of air between the structural gaps and spaces, forming “air cushion”, reducing contact area of corrosion medium and substrate. The Cassie contact mode hinder the corrosion media infiltrating and diffusing to the substrate. What’s more, the extremely low surface energy and surface adhesion make it hard for biological organisms to settle, mitigating the happening of biofouling. All experimental results in this thesis demonstrate that bio-inspired superhydrophobic surface on metallic or alloy substrates can provide an efficient solution strategy for marine environmental corrosion and biofouling problems, which is a promising protection technology.
学科领域海洋科学 ; 材料表面与界面
语种中文
文献类型学位论文
条目标识符http://ir.qdio.ac.cn/handle/337002/136574
专题海洋腐蚀与防护研究发展中心
作者单位中国科学院海洋研究所
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张斌斌. 铝基仿生超疏水界面的构筑及性能[D]. 北京. 中国科学院大学,2017.
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