阳极氧化法制备二氧化钛氧化膜耐海水腐蚀性能研究
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摘要
伴随着生产力的发展和科学技术的进步,海洋与人类的关系已经越来越密切,与此同时,大量的金属材料被应用在海洋科技研究与工程开发项目中。然而由于海水的高盐度及海洋气候本身特征导致了金属材料在海洋中的腐蚀相当严重。如何制备出新型的海洋材料来有效的防止金属在海水中的腐蚀成为当前各国科研机构研究的重要课题。本文在采用阳极氧化法制备出二氧化钛氧化膜的基础上,通过对其本身性质检测及其与高分子材料结合制备复合材料,旨在研究耐腐蚀薄膜的耐海水腐蚀性能,减缓材料表面腐蚀的发生,探索和研究出一种能够应用于海洋环境的耐腐蚀材料。
首先,我们使用硫酸作为电解液,以恒压阳极氧化方式在钛基体上制备二氧化钛氧化膜,利用XRD表征了不同条件下制备的氧化物膜的结构,利用接触角测量仪和扫描电镜等测试方法研究了二氧化钛氧化膜的亲疏水性及其表面结构；使用电化学阻抗、极化曲线进行耐腐蚀性能分析。实验结果表明,阳极氧化制备出的二氧化钛氧化膜具有较好的耐海水腐蚀性能,而二氧化钛黑暗条件下特有疏水性能进一步增加了氧化膜的耐腐蚀性。
其次,我们使用恒电位法在制备好的二氧化钛氧化膜上聚合一层聚苯胺膜。使用SEM、接触角测定仪检测聚苯胺的表面形貌和疏水性能；使用电化学阻抗,极化曲线等电化学测试方法对其进行耐腐蚀性能测试。实验结果表明,在弱碱性海水中,聚苯胺还原单元去掺杂,生成全氧化态聚苯胺,全氧化态聚苯胺拥有优异的耐海水渗透和耐腐蚀性能,因此有效的增加对内部金属的保护,这对降低金属的腐蚀速率有显著的作用。
第三,我们采用聚苯乙烯球作为表面修饰材料,在已经生成好的二氧化钛纳米管氧化膜上制备出聚苯乙烯球/二氧化钛纳米管复合膜,使用接触角测定仪和电化学阻抗,极化曲线测试方法来分别测试其疏水性和耐海水腐蚀性能。实验结果表明,疏水材料修饰的氧化膜表面能够有效的阻止海水向氧化膜内部的渗透,从而降低海水对氧化膜的腐蚀性能。
With the development of productivity and modern technology, the relationship between human and ocean were reinforced by the human exploitations and research activities. Meanwhile, thousands of metal materials with different type and properties were used in the marine scientific research and oceanic engineering. However, these metal materials may be corroded by seawater solution and the special marine environment, urgent research works on developing corrosion resistant material is a task for academic institutions. Based on the excellent physical and chemical properties of TiO2 film, we want to make full use of the preparation condotions, also with some excellent corrosion resistant polymer materials in the oceanic environment. The TiO2 film may inhibit a direct contact between the metal and solution, high polymers also can change the surface hydrophobicity, reducing sloution penetration, increasing material's corrosion resistance.
First, TiO2 films were formed on metallic titanium substrates by anodic oxidation method in H2SO4 solution. Component, microstructure and hydrophobic properties were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and water contact angle tester; electrochemical properties were researched through electrochemistry impedance spectrum(EIS) and polarization curves. The result showed that the TiO2 film prepared by anodic oxidation method owned better corrosion resistance, and its hydrophobic property in dark condition increase corrosion resistance in seawater solution.
Second, PANI/TiO2 compostie films were prepared on metallic titanium substrates by potentiostatic method in H2SO4/An solution. Microstructure and hydrophobic properties were characterized by scanning electron microscopy (SEM) and water contact angle tester; electrochemical properties were researched through electrochemistry impedance spectrum (EIS) and polarization curves. The result showed that the PANI/TiO2 compostie film prepared by potentiostatic method owned better hydrophobic property and corrosion resistance in alkalescent seawater, and it decreased the metal corrosion rate greatly.
Third, in order to increase the surface hydrophobicity, polystyrene sphere was used in this part. Using chemical and physical methods to cover a thin hydrophobic surface on TiO2 which prepared by anodic oxidation method. Water contact angle method and electrochemical method were used to test their hydrophobic properties and corrosion performances. The result showed that oxidation film modified by hydrophobic materials can isolate seawater penetrate into the surface effectively, hence reduce corrosion effects seawater caused.
首先,我们使用硫酸作为电解液,以恒压阳极氧化方式在钛基体上制备二氧化钛氧化膜,利用XRD表征了不同条件下制备的氧化物膜的结构,利用接触角测量仪和扫描电镜等测试方法研究了二氧化钛氧化膜的亲疏水性及其表面结构；使用电化学阻抗、极化曲线进行耐腐蚀性能分析。实验结果表明,阳极氧化制备出的二氧化钛氧化膜具有较好的耐海水腐蚀性能,而二氧化钛黑暗条件下特有疏水性能进一步增加了氧化膜的耐腐蚀性。
其次,我们使用恒电位法在制备好的二氧化钛氧化膜上聚合一层聚苯胺膜。使用SEM、接触角测定仪检测聚苯胺的表面形貌和疏水性能；使用电化学阻抗,极化曲线等电化学测试方法对其进行耐腐蚀性能测试。实验结果表明,在弱碱性海水中,聚苯胺还原单元去掺杂,生成全氧化态聚苯胺,全氧化态聚苯胺拥有优异的耐海水渗透和耐腐蚀性能,因此有效的增加对内部金属的保护,这对降低金属的腐蚀速率有显著的作用。
第三,我们采用聚苯乙烯球作为表面修饰材料,在已经生成好的二氧化钛纳米管氧化膜上制备出聚苯乙烯球/二氧化钛纳米管复合膜,使用接触角测定仪和电化学阻抗,极化曲线测试方法来分别测试其疏水性和耐海水腐蚀性能。实验结果表明,疏水材料修饰的氧化膜表面能够有效的阻止海水向氧化膜内部的渗透,从而降低海水对氧化膜的腐蚀性能。
With the development of productivity and modern technology, the relationship between human and ocean were reinforced by the human exploitations and research activities. Meanwhile, thousands of metal materials with different type and properties were used in the marine scientific research and oceanic engineering. However, these metal materials may be corroded by seawater solution and the special marine environment, urgent research works on developing corrosion resistant material is a task for academic institutions. Based on the excellent physical and chemical properties of TiO2 film, we want to make full use of the preparation condotions, also with some excellent corrosion resistant polymer materials in the oceanic environment. The TiO2 film may inhibit a direct contact between the metal and solution, high polymers also can change the surface hydrophobicity, reducing sloution penetration, increasing material's corrosion resistance.
First, TiO2 films were formed on metallic titanium substrates by anodic oxidation method in H2SO4 solution. Component, microstructure and hydrophobic properties were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and water contact angle tester; electrochemical properties were researched through electrochemistry impedance spectrum(EIS) and polarization curves. The result showed that the TiO2 film prepared by anodic oxidation method owned better corrosion resistance, and its hydrophobic property in dark condition increase corrosion resistance in seawater solution.
Second, PANI/TiO2 compostie films were prepared on metallic titanium substrates by potentiostatic method in H2SO4/An solution. Microstructure and hydrophobic properties were characterized by scanning electron microscopy (SEM) and water contact angle tester; electrochemical properties were researched through electrochemistry impedance spectrum (EIS) and polarization curves. The result showed that the PANI/TiO2 compostie film prepared by potentiostatic method owned better hydrophobic property and corrosion resistance in alkalescent seawater, and it decreased the metal corrosion rate greatly.
Third, in order to increase the surface hydrophobicity, polystyrene sphere was used in this part. Using chemical and physical methods to cover a thin hydrophobic surface on TiO2 which prepared by anodic oxidation method. Water contact angle method and electrochemical method were used to test their hydrophobic properties and corrosion performances. The result showed that oxidation film modified by hydrophobic materials can isolate seawater penetrate into the surface effectively, hence reduce corrosion effects seawater caused.
引文
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[2]顾家琳,闫睿,久本淳,濑文雄.碳钢在青岛不同暴露方式下的大气腐蚀.材料工程,2009,(12)：37～41
[3]J.L. Alamilla, M.A. Espinosa-Medina and E. Sosa. Modelling steel corrosion damage in soil environment. Corrosion Science,20095,51(11):2628～2638
[4]A.M.Abdel-Gaber, E.Khamis, H.Abo-ElD,Sh.Adeel. Inhibition of aluminium corrosion in alkaline solutions using natural compound. Materials Chemistry and Physics,2008,109(2): 297～305
[5]D. Delafosse and T. Magnin. Hydrogen induced plasticity in stress corrosion cracking of engineering systems,2001,68(6):693～729
[6]X.T. Chang, Y.S. Yin. G.H. Niu, T. Liu, S. Cheng and S.B. Sun.The Electrochemical Behavior of Oceanic Microbiological Influenced Corrosion on Carbon Steel. Acta Metallurgica Sinica (English Letters),2007,20(5):334～340
[7]吴宇新,宋晓杰,黄一,张崎.李欣.基于非线性均匀腐蚀理论的抗冰海洋平台疲劳分析.中国海洋平台,2008,(5)：15～18
[8]Adil Jarrah, Jean-Marie Nianga, Alain lost, Gildas Guillemob and Denis Najjar. On the detection of corrosion pit interactions using two-dimensional spectral analysis, Corrosion Science.2010,52(2):303～313
[9]Rong Xue, Yuan-Yuan Qian, Ke-Ke Liu, Xiao-Xing Jiang, Jun-Jie Zhu and Jian-Rong Zhang.Nano-pit corrosion of the tabs in aluminum electrolytic capacitor:Polarization characteristics of the tabs in ethyleneglycol-borate solution with chloride ions. Corrosion Science, 2008,50(10):2779～2784
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