【作者】 刘涛；

【导师】 尹衍升；

【作者基本信息】 中国海洋大学 ， 海洋化学工程与技术， 2009， 博士

【摘要】 人类已经进入海洋开发的新时代,海洋资源开发、海上运输、海港和海防建设等领域都需要大量的专用新型材料和新型表面防护技术,研究这些材料的制备科学和工艺技术、失效机制、探索未来海洋开发所需求的新概念表面防护理论和应用领域预测显得格外重要和迫切。而在金属基体上构建超疏水表面是近年来表面防护技术的一个新兴领域,因此,研究不同金属基体（包括金属间化合物基体）超疏水表面的制备,以及其超疏水表面的海洋防腐蚀与防生物污损功能将对海洋表面防护技术的进一步发展有着深远的影响。本课题以不同类型金属（包括铜,铝及铁铝金属间化合物）为研究对象,利用分子动力学模拟和量子化学计算相结合的方法首先确定适合不同金属的超疏水表面制备方法和制备体系,在铜表面使用表面自组装法构建十四烷酸分子层;对于金属铝,则先进行阳极氧化,在表面构建适合的微观粗糙度,再浸泡于十四烷酸溶液中进行组装;而对于铁铝金属间化合物,由于其特殊的组成结构,可以使用双层沉积法,先以物理吸附在材料表面形成一层单分子层,再在此分子层上嫁接十四烷酸分子层。这三种方法主要针对不同金属表面结构而定,既相互联系,又有明显不同。利用原子力显微镜,扫描电镜,椭圆偏振光测量仪,接触角测量仪等手段对超疏水表面进行表征,发现在不同金属基体上利用不同方法制备的超疏水表面,其微观形貌有很大区别,在铜表面是类似于花瓣状结构,铝表面则为树叶状结构,而铁铝金属间化合物表面则为类似于荷叶表面的乳突结构,虽然三种金属表面形貌各异,但都满足一定的表面粗糙度,这也是超疏水表面形成的必备条件之一;进而通过电化学手段对不同金属表面超疏水膜的抗海水腐蚀能力进行横向与纵向的评测,经动电位极化曲线分析得出,超疏水膜的存在,使阳极和阴极电流都明显减小,腐蚀电位E_Corr正方向移动,说明超疏水表面的存在阻止了金属基体的阳极溶解过程。Nyquist与Bode谱解析与等效电路数据拟合显示,超疏水表面对于铜,铝,铁铝金属间化合物的缓蚀效率可分别达到99%,97%和86%。说明超疏水表面的形成有效阻止了海水对于金属材料表面的侵蚀。另外,确立超疏水表面的抗腐蚀模型,并探讨其抗腐蚀机理。最后,通过静态挂片法获得三种金属在青岛天然海水中浸泡不同时间后表面的优势菌种,经过生物方法PCR鉴定获悉,优势菌种为需钠弧菌。采用比浊法测定细菌的生长曲线,明确了该细菌在培养条件下的生长规律。进而通过挂片实验和荧光显微镜观察,证明了超疏水表面可明显抑制海洋微生物的附着。更多还原

【Abstract】 The ocean epoch is coming, the marine materials and the technic of surface protection are urgent needed in the area of exploitation of marine resources, transport in ocean and marine engineering. Because of interesting properties and important applications in fundamental researches and industrial applications, super-hydrophobic surface has attracted significant attention, and various fabrication methods have been reported. However, to the best of our knowledge, little attention has been paid to super-hydrophobic surface equipped with anticorrosion properties to metallic surface. Such surface is of great importance for many industrial applications, and may present a solution to the long-standing problems of environmental contamination and corrosion of metals and metal alloysA novel super-hydrophobic film was prepared by myristic acid （n-tetradecanoic） chemically adsorbed onto the copper wafer. The film formation and its structure were characterized by means of water contact angle measurement, Fourier transformation infrared spectroscopy （FTIR） and scanning electron microscopy （SEM）. The static contact angle for water on the surface of this organic film was measured to be as high as 158·.The formation of a composite interface composed of the flower-like surface nanostructures, water droplet and air trapped in the crevices was suggested to be responsible for the superior water-repellent property. The corrosion behavior of the super-hydrophobic surface was investigated with potentiodynamic polarization measurements and electrochemical impedance spectroscopy. Due to the‘air valleys’and‘capillarity’effects, the corrosion resistance of the material was improved remarkably.A novel and stable super-hydrophobic film was prepared by myristic acid (CH₃（CH₂）₁₂COOH, mya) chemically adsorbed onto the anodized aluminum surface. The static contact angle for seawater on the surface was measured to be 154o. As evidenced by molecular dynamics （MD） simulations and electrochemical impedance spectroscopy （EIS）, the effect of ethanol solvent on the film stability was proved. The surface structure and composition were then characterized by means of scanning electron microscopy （SEM） with energy dispersive X-ray spectrum （EDS） and atomic force microscope （AFM）. The electrochemical measurements showed that the super-hydrophobic surface significantly decreased the corrosion currents densities （icorr）, corrosion rates and double layer capacitance （Cdl）, as simultaneously increased the values of polarization resistance （Rct） of aluminum in sterile seawater.A super-hydrophobic film was prepared by myristic acid (CH₃（CH₂）₁₂COOH chemically adsorbed onto the polyethyleneimine （PEI） coated Fe₃Al-type intermetallic wafer. The film character and structure were probed with contact angle measurement, scanning electron microscopy （SEM） and atomic force microscope （AFM）. The results suggested that the structure of the film is similar to lotus and the seawater contact angle was larger than 150·. Moreover, the corrosion resistances of untreated and modified samples in seawater were investigated by electrochemical impedance spectroscopy （EIS）. Experimental results showed that the corrosion rate of Fe3Al-type intermetallic with super-hydrophobic surface decreases dramatically because of its special microstructure.In addition, the preponderant bacterium was obtained from the surfaces of copper, aluminum and Fe3Al-type intermetallic which were staticly hung in natural sea water from Qingdao for different times. The preponderant bacterium was identified as Vibrio natriegens （V. natriegens） through biological method namely PCR. The survival habit and growth curve were studied using nephelometery. Moreover, the effect on microbial attachment of superhydrophobic surface was discussed using fluorescence microscope.更多还原