基于sol-gel电化学技术的超疏水表面及其在金属防护中的应用

发布时间：2018-06-10 10:02

本文选题：电沉积 + 硅烷　；参考：《浙江大学》2017年博士论文

【摘要】：润湿性是材料表面的重要性能之一,取决于材料表面的微纳结构以及表面自由能的大小。超疏水表面是一种与水滴接触角大于150°且滚动角小于10°的特殊材料表面。在自然界中,超疏水现象无处不在,如荷叶"出淤泥而不染"、水黾在水面上可以自由驰骋等。深入研究荷叶结构发现,在微观结构上,荷叶表面由微米级的乳突构成,同时乳突上还有很多树枝状的纳米结构,这些微纳米结构表面均由低表面能的生物蜡所覆盖。受荷叶结构启发,人们设计出两种超疏水表面的制备方法:一、将具有低表面能的物质表面粗糙化;二、采用低表面能物质修饰粗糙的材料表面。目前,人们已经开发出很多制备超疏水表面的方法,如水热法、刻蚀法、化学气相沉积法、电沉积法,静电纺丝法等。其中,电化学辅助沉积法以其可控性强、易于重复等特点而被广泛地应用在电分析、传感器、金属腐蚀防护、超疏水薄膜制备等领域。本论文利用电化学辅助沉积技术在金属基体上构建超疏水表面,研究其对金属腐蚀防护功能;利用超疏水粗糙多孔的结构作为缓蚀剂存储器构建具有主动防护功能的超疏水薄膜;通过采用低表面能聚合物交联修饰或者超疏水纳米颗粒填充的方法,改善电沉积超疏水溶胶-凝胶(sol-gel)薄膜的机械耐磨性能。本论文主要研究工作包括:(1)金属基体上电沉积超疏水sol-gel薄膜以及耐蚀性能研究。分别采用"一步"电沉积技术和"两步法"制备得到超疏水sol-gel薄膜,并采用接触角变化、铁离子溶出量和电化学阻抗谱(EIS)研究了超疏水薄膜的防护性能。研究表明,超疏水处理的基体,其耐蚀性能明显得到提高,相对于"一步法"而言,由于电沉积无机SiO2薄膜的刚性强,使得"两步法"制备所得超疏水薄膜的机械性能和热修复性能均略胜一筹。(2)构建具有主动防护功能的超疏水薄膜及其相关研究。利用电沉积sol-gel薄膜粗糙多孔的结构特点,将其作为缓蚀剂的载体构建具有主动防护功能的超疏水表面。针对无机、有机两种不同类型的缓蚀剂,采用了两种不同的缓蚀剂包裹方法。对于不溶于后续低表面能物质中的无机铈盐缓蚀剂,采用分步制备的方法,即先吸附无机缓蚀剂后修饰以低表面能物质,得到含有铈盐的超疏水薄膜;对于易溶于低表面能物质溶液中的有机缓蚀剂苯并三氮唑(BTA),则采用在前驱体溶液中加入缓蚀剂,通过一步电沉积的方法制备含有缓蚀剂的复合超疏水薄膜,BTA释放动力学曲线测试结果表明,金属腐蚀所引起的局部pH的变化可以有效地引发缓蚀剂的释放。研究结果表明:无机/有机缓蚀剂的加入可以进一步降低金属的腐蚀速率,提高基体的耐蚀性能。(3)利用聚合物PDMS修饰或超疏水二氧化硅纳米颗粒填充的方法构建耐磨超疏水表面。采用PDMS作为修饰剂时,PDMS用量的过少时,薄膜的疏水性和耐磨性均不佳,而过量的PDMS又会覆盖电沉积SiO2的粗糙结构。适量的PDMS可以在保证良好超疏水性的同时有效地交联电沉积Si02颗粒,减缓超疏水表面在摩擦过程中受到的机械损伤。采用电泳的方式将超疏水SiO2颗粒填充在整个电沉积SiO2的多孔骨架中,从而制备得到超疏水薄膜,该薄膜兼具电沉积Si02刚性结构和超疏水Si02颗粒的超疏水性。和(2)中"两步法"超疏水薄膜相比,上述两种超疏水表面的耐机械摩擦性得到明显提高。此外超疏水Si02纳米颗粒填充的超疏水薄膜还具有优异的热水性、耐高温性以及自清洁性。
[Abstract]:Wettability is one of the most important properties of the surface of the material, depending on the microstructure of the surface of the material and the size of the surface free energy. The superhydrophobic surface is a special material surface with the contact angle greater than 150 degrees and the rolling angle less than 10 degrees. In nature, the superhydrophobic phenomenon is everywhere, such as the lotus leaf "out of silt without dyeing", and water on the surface of the water On the micro structure, the surface of the lotus leaf is made up of micrometer mastoid process, and there are also a lot of dendritic nanostructures on the mastoid process. These micro nanostructures are covered by low surface energy paraffin. Inspired by the lotus leaf structure, two kinds of superhydrophobic surfaces are designed. Preparation methods: first, the surface of material with low surface energy is rough; two, using low surface energy to modify the surface of rough materials. At present, many methods have been developed to prepare superhydrophobic surfaces, such as hydrothermal, etching, chemical vapor deposition, electrodeposition, electrospinning, etc. Strong control, easy to repeat and so on, it is widely used in the fields of electrical analysis, sensors, metal corrosion protection, and super hydrophobic film preparation. This paper uses electrochemical auxiliary deposition technology to construct superhydrophobic surface on metal matrix, and studies its protective function for metal corrosion; it uses super hydrophobic and porous structure as a corrosion inhibitor. A superhydrophobic film with active protective function is constructed in the reservoir, and the mechanical wear resistance of Electrodeposited superhydrophobic sol-gel (sol-gel) film is improved by means of low surface energy polymer crosslinking modification or superhydrophobic nanoparticles filling. The main research work includes: (1) electrodeposition of superhydrophobic sol-gel thin on the metal matrix Super hydrophobic sol-gel film was prepared by "one step" electrodeposition and two step method respectively. The protection performance of super hydrophobic film was studied by the change of contact angle, iron ion dissolution and electrochemical impedance spectroscopy (EIS). The study showed that the corrosion resistance of the superhydrophobic matrix was obviously improved, and the relative corrosion resistance of the superhydrophobic film was obviously improved. In the one step method, the mechanical properties and heat repair properties of the super hydrophobic film prepared by the "two step method" are slightly better than that of the electrodeposited inorganic SiO2 film. (2) the construction of super hydrophobic film with active protection function and its related research. The carrier of the corrosion agent constructs a super hydrophobic surface with active protective function. For inorganic and organic two different types of corrosion inhibitors, two different inhibitors are used. For the inorganic cerium salt corrosion inhibitor insoluble in the subsequent low surface energy, the step preparation method, that is, after the adsorption of inorganic corrosion inhibitor, is low. The superhydrophobic film containing cerium salts is obtained by the surface energy. For the organic corrosion inhibitor, benzo three azoles (BTA), which is easily dissolved in the solution of low surface energy, the inhibitor is added to the precursor solution, and the composite superhydrophobic film containing corrosion inhibitor is prepared by one step electrodeposition. The test results of the BTA release kinetics curve show that The change of local pH caused by metal corrosion can effectively lead to the release of corrosion inhibitor. The results show that the addition of inorganic / organic corrosion inhibitor can further reduce the corrosion rate of metal and improve the corrosion resistance of the matrix. (3) the use of polymer PDMS modification or superhydrophobic two silicon oxide nanoparticles filling method to construct the wear-resistant super sparse method Water surface. When PDMS is used as a modifier, the hydrophobicity and wear resistance of the film are not good when the amount of PDMS is too little. The excess PDMS will cover the rough structure of the electrodeposition of SiO2, and a proper amount of PDMS can effectively cross link the electrodeposited Si02 particles at the same time to ensure the good superhydrophobicity, and slow down the superhydrophobic surface during the friction process. Mechanical damage. Superhydrophobic SiO2 particles are filled in the porous framework of the entire electrodeposited SiO2 by electrophoretic method, and the superhydrophobic film is prepared. The film has the superhydrophobicity of both the electrodeposited Si02 rigid structure and the super hydrophobic Si02 particles. Compared with the "two step" superhydrophobic film in (2), the mechanical friction of the above two superhydrophobic surfaces In addition, superhydrophobic Si02 nanoparticles filled superhydrophobic films also have excellent thermal properties, high temperature resistance and self cleaning properties.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TG174.4

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