【作者】 王杰；

【导师】 曹楚南； 张昭；

【作者基本信息】 浙江大学 ， 化学， 2011， 硕士

【摘要】 金属材料是现代社会中使用最广泛的工程材料,在人类的文明与发展方面起着十分重要的作用。我国的金属腐蚀情况是很严重的,特别是我国对金属腐蚀的保护工作与发达的工业国家相比还有一段距离。金属腐蚀在造成经济损失的同时,也造成了资源和能源的浪费——由于所报废的设备或构件有少部分是不能再生的,可以重新冶炼再生的部分在冶炼过程中也会耗费大量的能源,因此对金属防护研究是利国利民的选择。针对国内外钢铁的腐蚀防护现状,本论文工作分为两个部分。第一部分是基于电沉积过程中的“外延生长”和“诱导成核”等理论,采用电化学方法和纳米晶前驱诱导物来制备纳米晶Ni-TiN薄膜材料,制备出性能优良的纳米薄膜材料,在实验室前期研究的基础上继续开拓一种全新的纳米材料制备方法。第二部分是采用亚麻籽油制备双酚A环氧树脂添加剂,利用其碳碳双键、酰胺键和羟基与环氧树脂中的环氧键发生交联,提高环氧涂层的交联度并增加涂层的防护性能。论文首先研究了Ni-TiN电沉积的主要工艺参数(主盐金属离子、硼酸和添加剂的浓度、pH值、温度、电镀电流密度和搅拌速度等)对纳米晶Ni-TiN薄膜的结构和性能的影响规律；最终优化出一套制备纳米晶Ni-TiN薄膜的稳定、可靠的电沉积工艺。在上述基础上,采用SEM、TEM、AFM和XRD等技术对在优化工艺下制备的Ni-TiN纳米复合薄膜的表面形貌和结构进行了表征,同时对纳米晶Ni-TiN复合薄膜和传统多晶纯镍镀层的微观硬度、耐蚀性能和热稳定性等进行了对比研究。结果表明,纳米晶Ni-TiN复合薄膜表面平整、其连续的Ni基体相和离散的TiN添加相均具有纳米结构,复合薄膜的晶粒平均粒径为70-80 nm；由于TiN纳米粒子的共沉积,使得镍镀层晶粒得到细化,这提高了镀层的性能,纳米复合镀层的优点得到体现。中试表明,该纳米晶Ni-TiN复合薄膜的电镀工艺稳定,有良好的实际应用前景。论文的第二部分采用亚麻籽油制备了双酚A环氧树脂添加剂,利用合成的添加剂中各官能团与双酚A环氧树脂发生交联反应,制备出了改性的环氧树脂涂层。采用CHI电化学工作站、电化学阻抗(EIS)和热重分析仪对涂层性能进行了测试,并研究了涂层中添加剂的量对涂层性能的影响规律,确定其最佳用量值；同时,将改性的环氧树脂涂层与其他油气田用重防腐涂料对油田用钢的防护性能进行了对比研究。结果表明,加入添加剂后,涂层的防腐和热稳定性能显著提高；涂层的综合性能随添加剂量的增加而提高,但混合的添加剂量超过一定数值后,改性环氧涂层的性能开始下降；通过与其他重防腐涂料的对比研究发现,本论文制备的改性环氧涂层的孔隙率相对较高,这影响了其防腐性能的进一步提升,也为我们下一步的研究提供了方向。更多还原

【Abstract】 Metal has been the most widely used material in this modern society, which plays an important pole in the civilization and development of the human. Corrosion of metals is very serious in China. What is worse, the technology of protection of metal is far from that of the developed countries. Corrosion of metals not only caused economic losses, but also made the wasting of resources and power. Therefore, the research of protection of metal is an activity that benefits the nation and the people.Based on the theories of "epitaxial growth" and "derivational nucleation", this dissertation tries to adopt a modification method based on traditional composite electroplating technique and a few of nano-TiN particle predecessors has been developed to fabricate the holistically nanostructured Ni-TiN films. The research not only has value in theory, but also has an expansive applied foreground. Meanwhile, N,N-bis(2-hydroxyethyl) linseed amide(HELA) which was prepared by linseed oil was used as modifier for conventionally available epoxy resin(DGEBA) to improve the performance of resin by cross-linked reaction between them.Firstly, this paper studied the influences of principal technological parameters on the microstructure of eletrodeposited Ni-TiN nanocomposite film. Such as:the concentration of metal ion and boric acid, current density, pH value, temperature, solution agitation speed and so on. We optimized a steady technics ultimately. Secondly, the microstructure and feature of the optimized nanostuctured Ni-TiN composite film was characterized by scanning transmission electron microscopy (SEM), atomic force microscope (AFM), transmission electron microscope (TEM) and X-ray(XRD).It can be clearly seen that the optimized nanostuctured Ni-TiN composite film is composed of the nanoparticles with the average grain sizes in the nanometer range, which proves that the as-obtained nanostuctured Ni-TiN composite film is substantially nanostructured in character, and the average diameter of Ni grains of the composite coatings is approximately equal to 70-80nm. Third, the anti-corrosion properties, hardness and thermostability of Ni-TiN nanocomposite films were also investigated and compared with the traditional polycrystalline Ni coatings. The results show that, compared with the traditional polycrystalline Ni film, Ni-TiN nanocomposite coatings display much better corrosion resistance, higher film hardness, and thermal stability. In addition, the hardness and anti-corrosion of Ni-TiN nanocomposite coatings decreases slightly with the increase of electroplating current density, which may be due to the synergism of hydrogen evolution and faster nucleation/growth rate of nickel crystallites.On the other hand, due to hydrogen bonding and chemical reaction between the epoxy resin and HELA, the modified epoxy was prepared in this paper. DGEBA/HELA blends were further treated with triethylenetetramine as curing agent to evaluate their thermostability and other performance as corrosion protective coating materials. DGEBA/HELA coatings showed good thermostability and corrosion resistance behavior. The investigations confirmed the dual role of HELA as environment-friendly, reactive-modifier and mild curing agent for epoxy resins. Compared with other anti-corrosive paints, we found that total porosity of modified epoxy coating was relatively high, which influenced the performance of coating and gave us the next research direction to improve the property of DGEBA/HELA coatings.更多还原