碳钢论文：碳钢表面杂化膜的制备及防腐性能研究.doc

碳钢论文：碳钢表面杂化膜的制备及防腐性能研究【中文摘要】碳钢,因其良好的机械可加工性能和低廉的价格被广泛应用于机械、建筑等各个领域。由于碳钢本身的耐腐蚀性能很差,在应用过程中,常常需要对其进行适当的表面处理来增加使用寿命。传统的表面处理工艺中,磷化和铬化展现出良好的防腐效果。但是,磷化、Cr（VI）有致癌和对环境有持久危险性。随着社会的发展,不久的将来,铬化和磷化在表面处理中的应用将会被禁用。因此,绿色环保、价格低廉的新型表面处理工艺的研究是一项非常有意义的工作并且成为国内外研究的焦点。为了制备以硅烷为主体的杂化膜,本论文首先研究了双-四硫化物硅烷（油基硅烷）和乙烯基三甲氧基硅烷（水基硅烷）两种不同硅烷在碳钢表面的最佳成膜工艺。利用扫描电镜（SEM）、（EDS）等测试手段对硅烷膜的形貌和构成进行了表征。结果表明:两种硅烷均能在Q235碳钢表面形成比较均匀完整的硅烷膜。利用动电位极化曲线和电化A学阻抗（EIS）测试手段,研究了碳钢表面两种不同的硅烷膜在模拟海水中的电化学行为。结果表明:在短期内,两种硅烷膜都对碳钢有较好的防护效果,双-四硫化物硅烷膜效果更佳。但是不足之处在于,单一的硅烷膜同其它的有机膜一样,耐蚀性能不理想,不能对碳钢起到较长期的保护作用。硅烷膜膜层很薄,并且在碳钢表面形成的是一种空间网络状结构,这种结构给一些无机纳米级颗粒提供了一定的填充空间。也就是说,通过硅烷与纳米级无机盐或氧化物共同作用,能够在碳钢表面生成一层更加致密,完整的有机/无机杂化膜。此外,我们知道:变价金属添加到涂层或膜中,能使膜或涂层产生一种自修复功能。铈是变价金属。硝酸铈盐常温下既能溶于水,也能溶于无水乙醇,并且无毒,价格不高;而正硅酸乙酯与硅烷共混可形成无相分离的溶胶,这就给我们的实验提供了一个很好的平台。针对上述的不足与优势,我们利用双-四硫化物硅烷（油基硅烷）和乙烯基三甲氧基硅烷（水基硅烷）分别与硝酸铈盐复配,在碳钢表面制备了两种不同的硅烷/铈盐杂化膜。扫描电镜（SEM）结果显示:硝酸铈与水基的乙烯基三甲氧基硅烷共同作用生成的杂化膜中填充颗粒粒径在90纳米左右;而硝酸铈与油基的双-四硫化物硅烷共同作用生成的杂化膜中填充颗粒粒径在40-50纳米之间。EDS结果表明:Ce确实是杂化膜的构成元素之一。动电位极化曲线和电化学阻抗（EIS）结果均表明:杂化膜对碳钢的防腐效果好于单独的硅烷膜,但是效果不是很明显;双-四硫化物硅烷与硝酸铈共同作用形成的杂化膜的防腐效果要好于乙烯基三甲氧基硅烷与硝酸铈共同作用形成的杂化膜的防腐效果。与乙烯基三甲氧基硅烷相比,双-四硫化物硅烷更适合碳钢体系。为了进一步提高杂化膜的防腐性能,我们又初步探索了将正硅酸乙酯、双-四硫化物硅烷和硝酸铈共混,通过一步法,在碳钢表面制备杂化膜的工艺。动电位极化曲线、电化学阻抗（EIS）和3%CuSO4点滴实验说明,正硅酸乙酯的加入,的确提高了膜对碳钢的保护性能。【英文摘要】Carbon steel is widely used in engineering machinery and construction projects and various field because of its good machinability and low price. But it must be given appropriate suface treatment so as to prolong its working life on account of the poor corrosion resistance of carbon steel itself. Amang the traditional treatment, chromizing and phosphating present good properties of unticorrosion. However, chromizing and phosphating will be banned in the near future due to their uphold hazard to environment and carcinogenic to humans. So, it has truly significant and have been popular in home and abroad to study on the new suface treatment which have properties of efficient performance of unticorrosion and environment-friendly and low price.In order to prepare a kind of hybrid membrane, which was taken silane as the backbone,cerous nitrate and tetraethyl orthosilicate as additives. In this article, the optimum technics of the film prepared with bis-(-triethoxysilylpropyl)-tetrasulfide (BTESPT,oil-base silane) and vinyltrimethoxysilane (VTOS,water-base silane)on the carbon steel surface was studied first. The formation and surface structure of the film were characterized by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results indicate that two kinds of silane can form uniform and compact film on the Q235 carbon steel surface. The corrosion behaviour of the two silane films in the artificial simulated seawater was evaluated by potential dynamic polarization and electrochemical impedance spectroscopy (EIS). The results indicate, twe silane films both have better protect for carbon steel in short time. BTESPT film has better effect than VTOS film. As other organic films, the deficiency of the single silane film is that they havent corrosion resisting property, they cant play the role of anti-corrosion for long term.The strcture of silane film on the carbon steel surface is net type which provide some packing space for nano inorgannic particles. That is to say the hybrid membrane can be much compact and integrated through silane coorprate with inorgannic or oxide nano particles. In addition, the film will take on a function of self-repairing by the addition of variant valene metal. Cerium is a kind of variant valene metal. cerium nitrate can soluble both in water and ethanol absolute, it is asepsis and low-priced. Furthermore, tetraethyl orthosilicate (TEOS) has good compatibility with silane. These provide us a well platform for further experiment.Aim at the above-mentioned shortage and superiority, we employ vinyltrimetho- xysilane (VTOS ) and bis-(-triethoxysilylpropyl)-tetrasulfide(BTESPT) respectively coorperated with ceric ammonium nitrate. The results of potential dynamic polariza- tion and electrochemical impedance spectroscopy (EIS) show the nano particles in the hybrid membrane prepared with VTOS coorperated ceric ammonium nitrate is about 90 nm; the nano particles in the hybrid membrane prepared with BTESPT cerium nitrate is about 30nm. EDS show cerium is an element of the film-foming. The results of both potential dynamic polarization and electrochemical impedance spectro- scopy (EIS) indicate the effect unticorrosion for carbon of the hybrid membrane is better than single silane film,but not great obvious.Compared with VTOS, BTESPT is better fit for carbon systerm.In order to improve the antiseptic property of the hybrid membrane, the technics of hybrid membrane prepared with BTESPT/ Cerous nitrate/ TEOS mixing together through one step is initially explored. The outcome of potential dynamic polarization combined with EIS and 3% copper sulphate spot testing show, the addition of the TEOS indeed improve the protect property for carbon steel.【关键词】碳钢 杂化膜 电化学 耐蚀性【英文关键词】Carbon steel Hybrid membrane Electrochemistry Corrosion resistance【备注】索购全文在线加我：.8848 同时提供论文一对一写作指导和论文发表委托服务【目录】碳钢表面杂化膜的制备及防腐性能研究摘要5-7Abstract7-81 绪论13-301.1 金属腐蚀与防护技术概述13-201.1.1 碳钢的腐蚀机理研究14-161.1.2 传统的碳钢腐蚀与防护技术16-181.1.3 新型的碳钢腐蚀与防护技术181.1.4 膜技术的发展和研究现状18-201.1.5 膜技术中存在的问题、应用前景及最新发展动态201.2 硅烷偶联剂概述20-251.2.1 硅烷偶联剂的发展历史211.2.2 硅烷偶联剂的分类21-221.2.3 硅烷偶联剂的应用22- 硅烷偶联剂用作表面处理剂22- 硅烷偶联剂应用于复合材料中23- 硅烷偶联剂在涂料中的应用 硅烷偶联剂在金属表面预处理中的应用24-251.3 杂化膜概述25-261.3.1 杂化膜的制备技术251.3.2 杂化膜的应用25-261.4 电化学测试概述26-281.4.1 电化学测试概述261.4.2 电化学工作站的基本原理及应用26-2 交流阻抗的原理和应用26-2 动电位极化扫描27-281.5 本文的立体依据及主要研究内容28-301.5.1 本文的立体依据281.5.2 主要研究内容28-302 碳钢表面硅烷膜的制备及性能研究30-472.1 引言302.2 实验试剂、实验仪器和设备30-312.2.1 实验试剂30-312.2.2 实验仪器与设备312.3 硅烷膜的制备与表征31-332.3.1 碳钢试样的预处理312.3.2 不同浓度硅烷溶液的配置31-322.3.3 硅烷溶液水解时间的确定322.3.4 硅烷膜的制备322.3.5 碳钢表面硅烷膜的制备过程示意图32-332.4 VTOS 硅烷膜和BTESPT 硅烷膜的表征332.4.1 扫描电镜与能谱的表征332.4.2 电化学测试332.5 实验结果与讨论33-452.5.1 硅烷水解机理33-342.5.2 硅烷缩聚机理34-352.5.3 VTOS 硅烷溶液电导率随水解时间变化的表征分析35-362.5.4 VTOS 动电位极化曲线的分析36-392.5.5 不同体积比BTESPT 硅烷膜动电位极化曲线分析39-402.5.6 不同体积比BTESPT 硅烷膜EIS 曲线分析40-422.5.7 碳钢及硅烷膜表面形貌表征42-432.5.8 碳钢及硅烷膜元素分布43-442.5.9 pH 值对硅烷水解的影响44-452.5.10 硅烷在金属表面的成膜机理452.6 本章小结45-473 硅烷/铈盐杂化膜的制备及性能表征47-