CVD石墨烯改善铜抗腐蚀性能的研究

发布时间：2018-05-08 14:33

本文选题：石墨烯 + 常压化学气相沉积　；参考：《太原理工大学》2017年硕士论文

【摘要】：金属材料作为常用材料之一,在基础设施、交通运输等方面起着至关重要的作用。然而金属腐蚀现象却非常普遍,腐蚀行为会严重影响金属的使用寿命,给国民经济、工业发展带来巨大损失,甚至会威胁到人类的生命安全。因此,金属腐蚀问题成为现阶段亟待攻克的重大难题。然而,传统的防腐涂层大都耐温性差,会改变基体的理化性能,无法满足需求,故开发超薄且不影响基体性能的防腐涂层已成为金属防护领域的发展趋势。石墨烯是单层或少层碳原子构成的二维材料,是现阶段已发现材料中最薄的。石墨烯独特的六边形蜂巢状结构赋予了它诸多优异的性能,如很好的热、化学稳定性,优良的抗透性和机械性能等。因此石墨烯有望代替传统的防腐涂层成为新型的超薄防腐材料。CVD石墨烯虽然能在一定程度上保护金属基底不被侵蚀,但会不可避免地存在孔洞、晶界等结构缺陷,这些缺陷会削弱石墨烯对金属的保护作用。因此,对石墨烯缺陷进行钝化处理,进一步提高其耐蚀性能,可以实现石墨烯对金属的完全保护。本文采用常压化学气相沉积法(Atmospheric Pressure Chemical Vapor Deposition)在铜箔上制备石墨烯,并通过光学显微镜(Optical Microscope),扫描电子显微镜(Scanning Electron Microscopy),高分辨率透射电子显微镜(High Resolution Transmission Electron Microscopy),拉曼光谱仪(Raman)及紫外—可见分光光度计(UV-visible absorption spectroscopy)对石墨烯的形貌和结构分析表征,探究反应时间和甲烷流量对石墨烯生长的影响,找到APCVD制备石墨烯的最佳生长条件。结果表明,随着反应时间的延长,石墨烯趋于连续且层数增加。反应15 min时,石墨烯的层数达到三层,继续延长时间,层数不再增加,表现出一定的自限制性;当甲烷流量很小时,无法生成石墨烯,甲烷流量为2 sccm时,石墨烯开始生长,增大甲烷流量,石墨烯趋于连续且层数增加,甲烷流量增至10 sccm时,得到连续的三层石墨烯,继续增大甲烷流量,石墨烯的形核密度增大,其连续性变差。通过电化学法测试样品在0.1 M NaCl溶液中的抗电化学腐蚀性能,研究了石墨烯对铜抗腐蚀性能的改善作用及其作用机理。结果表明,单层石墨烯由于自身缺陷及连续性差,对铜没有保护作用,而连续少层石墨烯可以很好地保护铜不被腐蚀。其中,反应时间为15 min,甲烷流量为10 sccm时制得的三层石墨烯因缺陷少、连续性较好,抗腐蚀性能最好,比纯铜箔的抗腐蚀性能提高了1个数量级。进一步采用原子层沉积法(Atomic Layer Deposition)在石墨烯表面沉积三氧化二铝(Al2O3)钝化颗粒,对石墨烯的缺陷进行钝化处理,研究其对石墨烯改善铜抗腐蚀性能的影响。结果表明,石墨烯钝化处理后,石墨烯/铜样品的抗腐蚀性能得到了显著提高,单层、两层、三层石墨烯/样品的腐蚀电流密度比其钝化处理前的依次降低了80%、88%、56%,电阻依次增大了67.6、34.3、6.1倍。因此,对石墨烯的缺陷进行钝化处理,有望实现石墨烯对金属材料的完全保护。
[Abstract]:Metal materials, as one of the common materials, play an important role in infrastructure and transportation. However, the corrosion phenomenon of metal is very common. Corrosion behavior will seriously affect the life of metals, bring huge losses to the national economy and industrial development, and threaten the life safety of human beings. Therefore, metal corrosion is a serious problem. However, the traditional anticorrosion coatings are mostly poor in temperature resistance, which will change the physical and chemical properties of the matrix, and can not meet the needs. Therefore, the development of the anticorrosion coatings with ultra-thin and no influence on the matrix properties has become the development trend in the field of metal protection. It is the thinnest material found at the present stage. The unique hexagonal honeycomb structure of graphene has given it a lot of excellent properties, such as good heat, chemical stability, excellent anti permeability and mechanical properties. Therefore, graphene is expected to replace the traditional anticorrosion coating to become a new type of ultra-thin anticorrosion material.CVD graphene, although it can be in the same way. The metal substrate is not corroded to a certain extent, but it will inevitably have structural defects such as holes and grain boundaries. These defects will weaken the protective effect of graphene to metals. Therefore, the passivation of graphene defects can be passivated to further improve the corrosion resistance of graphene, and the complete protection of graphene to metals can be achieved. This paper uses atmospheric pressure chemistry. Atmospheric Pressure Chemical Vapor Deposition is used to prepare graphene on copper foil, and through optical microscopy (Optical Microscope), scanning electron microscope (Scanning Electron Microscopy), high resolution transmission electron microscope (High Resolution), Raman spectrometer and The morphology and structure of graphene were characterized by ultraviolet visible spectrophotometer (UV-visible absorption spectroscopy). The effect of reaction time and methane flow on the growth of Shi Moxi was investigated. The optimum conditions for the growth of graphene by APCVD were found. The results showed that with the prolongation of the reaction time, the number of graphene tended to be continuous and the number of layers increased. At 15 min, the number of graphene layers reached three layers, continued to extend the time, the number of layers no longer increased, showing a certain degree of self limiting. When the methane flow was very small, no graphene was generated and methane flow was 2 SCCM, the growth of graphene began to grow, the flow of methane increased, the number of graphene tended to increase and the methane flow rate increased to 10 SCCM. The continuous three layers of graphene will continue to increase the methane flow, the nucleation density of graphene increases and its continuity becomes worse. The electrochemical corrosion resistance of samples in 0.1 M NaCl solution is tested by electrochemical method. The effect of graphene on the corrosion resistance of copper and its mechanism are studied. The results show that the single graphene is due to its own defects. And the continuity is poor and has no protective effect on copper, while continuous few layers of graphene can protect copper not to be corroded. Among them, the reaction time is 15 min and the methane flow is 10 SCCM. The three layers of graphene have less defects, better continuity, better corrosion resistance, and 1 orders of magnitude higher than that of pure copper foil. Atomic Layer Deposition (Atomic) deposited two aluminum (Al2O3) passivating particles on the surface of graphene, passivating the defects of graphene, and studying its effect on the corrosion resistance of graphite to improve the corrosion resistance of copper. The results showed that the corrosion resistance of graphene / copper samples was greatly improved after the passivation of graphene. The corrosion current density of layers, two layers, three layers of graphene / sample decreased by 80%, 88%, 56%, and the resistance in turn increased by 67.6,34.3,6.1 times. Therefore, the defects of graphene were passivated, and the complete protection of graphene to metal materials was expected.

【学位授予单位】：太原理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TG174.4

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