水性锌铝粉防腐涂层的研究
摘要
进入21世纪以来,金属防护工业受到出于环保和节能等方面的日益严峻的压力,涂料工业向环保型发展已成定局。此外,对涂料性能和使用寿命的要求导致基于硅化学,碳、硅杂化化学等耐久性新一代聚合物日渐取代基于碳化学的聚合物,硅化学在几乎所有的涂料方面的渗透是显而易见的。
锌铬涂层(即达克罗DACROMET)属于水性金属粉涂层的范畴,是当今国际上金属表面处理富有代表性的技术。是一种同时具有物理屏蔽、阴极保护等优良防护功能的涂层,然而由于六价铬的毒性,目前世界各国尤其是发达国家已开始采取越来越严格的措施限制铬的使用。无铬锌铝涂层正是为满足世界各国的VOC法规和汽车行业规定的环保要求而开发出的表面处理新概念。目前美国、德国、日本、韩国已经有成型的无铬锌铝涂层面世。
本论文介绍了国内外传统锌铬涂层(即达克罗)的技术特点,总结概述了无铬锌铝涂层的发展及现状。在此基础上,尝试以无毒粘接剂及锌铝粉颜填料为主体,研制开发出环保型水性锌铝粉涂层,并且研究涂层的防护机理,尝试对涂层的性能进行改进。
论文从粘结剂的筛选入手,通过对涂层物理性能分析(附着力、涂层硬度等指标);以及涂层浸泡失效实验,选定硅烷作为锌铝粉涂层的粘结剂,制备了性能较好的水性锌铝粉涂层。硅烷用于金属粉涂层不仅可以起到粘结剂的作用,而且硅烷降低了锌粉的反应活性,抑制锌粉在涂层中的消耗。
运用扫描电镜(SEM),能谱分析(EDS)对制备的涂层表观形貌分析,得出涂层的组成结构为由层叠状结构的片状锌铝粉和硅烷粘结剂所组成,金属粉表面均匀的覆盖了一层硅烷膜,涂层表面存在微孔和缝隙。通过涂层/碳钢体系浸泡在3.5%NaCl中的EIS,以及极化曲线分析,分析了涂层的防腐机制,评价了涂层的防护性能。结果表明在整个浸泡过程中硅烷锌铝涂层主要出现了三个防护期,初期为表层锌铝粉的活化阶段,中期为锌铝粉的电化学保护阶段,后期为阻挡层保护阶段。中间阶段的持续时间最长,证明涂层的主要防护机制是金属粉的电化学保护。极化曲线出现了明显的类钝化现象,根据单独锌粉涂层,以及锌铝粉涂层的对比发现,这种类钝化现象的产生与铝粉没有直接的关系;结合锌铝粉涂层在浸泡失效过程中的极化曲线分析,得出这种类钝化现象的产生主要是因为锌粉的腐蚀产物造成的。
通过在涂液中添加无毒缓蚀剂来提高涂层的防护性能,并且通过电化学阻抗谱、极化曲线分析,得出缓蚀剂的作用机制,通过三种不同缓蚀剂的对比,筛选最佳的缓蚀剂。结果表明在涂液中添加缓蚀剂,明显增加了涂层的腐蚀电阻,降低了腐蚀电流,从而降低了锌铝粉的消耗速率,使得涂层的阴极防护期延长。在三种环保型缓蚀剂中,涂液中添加磷钼酸钠(Na_3PO_4·12MoO_4)使得涂层腐蚀电阻最大,腐蚀电流最小,涂层的防护性能提高的最大。
因为本论文是在相关文献很少的基础上自行研制水性金属粉涂层,并从事性能分析、性能改进等方面的研究。整个研究需要深入涉及的内容较多,因此要使该技术应用于实际工业生产,还有许多内容需要进一步地深入和完善。
Since 21~(th) century, anticorrosive industry is confront with the pressure from both environment-protection and energy-conservation. Silane-base treatments can replace the traditional treatments with remarkable advantages in relation to environmental, safety and costs issues.
The Dacromet coating with high corrosion resistance technology was a popular metal anticorrosion technology for many metals. Its applications in some fields such as automobile industry were getting increasingly common because of the advantages of less pollution, excellent anticorrosion property and non-hydrogen embrittlement. Since the conventional Dacromet treatment agent contains hexavalent chromium ions, which are hazardous, adverse effects on the human body, and environmental contamination, due to the elution of chromium from protective films have been a serious concern. Furthermore, legal restrictions have been imposed in various countries on the use of hexavalent chromium even in rust inhibitors for metallic surfaces. In response to society’s need for new, environmentally compatible products, many research has endeavored to develop new coating systems that are environmentally friendly. In the countries such as Germany、America、Japan and Korea ,many kinds of non-chromate zinc/Aluminium coating have developed.
The objective of this thesis is to develop an environmentally benign coating,which does not utilize harmful chromium compounds and can be used for corrosion inhibition of a metal surface, comprising a slurry mixture in which coated zinc and aluminum fine powder treated with a hydrophilic coupling agent is suspended in an silane bonding solution. The optimal conditions were screened out..Since the coating hasn’t any chromium ,and free of any other toxic compounds, it has friendly environmental performance. And because it composed of a large number of metal flakes, the coating is conductive. As the pre–processing of the coating doesn’t have acid washing, the coating is hydrogen embrittlement free.
The appearance of coating was observed and studied through microscope, SEM, and EDS. The result showed that: the coating combined with metal substrates tightly, and the thickness of coating was uniform. Corrosion potential and electrochemical impedance spectroscopy ( EIS) measurement s were used to study the corrosion electrochemical behavior of the modified coatings immersed in 3.5% NaCl solution. The results indicated that the process of action of the coating during immersion presented three stages. At the initial stage, the flaked zinc powder on the surface layer of the coating started to activate due to the attack of the electrolyte. In the middle stage, the coating exhibited electrochemical protection for the substrate. For the third stage, the barrier protection of the coating predominated. The middle stage lasted a longer period than the third stage, suggesting a strong cathodic protection and a weak barrier mechanism of corrosion prevention of the silane zinc–aluminum coating.
Further more, in this thesis, we also study the corrosion properties of the coating with three different inhibiting blended in definite proportion. The results indicated that the addition of inhibitors can improve the protection performance of the coating, mitigating the consumption of the zinc and aluminium powder in the coating. Among the three inhibitors phosphomolybdate is the best, while the effect of cerium chloride is better than that of sodium molybdate.
In order to put this process into industrial use, there are still many problems waiting for further research and amelioration.
锌铬涂层(即达克罗DACROMET)属于水性金属粉涂层的范畴,是当今国际上金属表面处理富有代表性的技术。是一种同时具有物理屏蔽、阴极保护等优良防护功能的涂层,然而由于六价铬的毒性,目前世界各国尤其是发达国家已开始采取越来越严格的措施限制铬的使用。无铬锌铝涂层正是为满足世界各国的VOC法规和汽车行业规定的环保要求而开发出的表面处理新概念。目前美国、德国、日本、韩国已经有成型的无铬锌铝涂层面世。
本论文介绍了国内外传统锌铬涂层(即达克罗)的技术特点,总结概述了无铬锌铝涂层的发展及现状。在此基础上,尝试以无毒粘接剂及锌铝粉颜填料为主体,研制开发出环保型水性锌铝粉涂层,并且研究涂层的防护机理,尝试对涂层的性能进行改进。
论文从粘结剂的筛选入手,通过对涂层物理性能分析(附着力、涂层硬度等指标);以及涂层浸泡失效实验,选定硅烷作为锌铝粉涂层的粘结剂,制备了性能较好的水性锌铝粉涂层。硅烷用于金属粉涂层不仅可以起到粘结剂的作用,而且硅烷降低了锌粉的反应活性,抑制锌粉在涂层中的消耗。
运用扫描电镜(SEM),能谱分析(EDS)对制备的涂层表观形貌分析,得出涂层的组成结构为由层叠状结构的片状锌铝粉和硅烷粘结剂所组成,金属粉表面均匀的覆盖了一层硅烷膜,涂层表面存在微孔和缝隙。通过涂层/碳钢体系浸泡在3.5%NaCl中的EIS,以及极化曲线分析,分析了涂层的防腐机制,评价了涂层的防护性能。结果表明在整个浸泡过程中硅烷锌铝涂层主要出现了三个防护期,初期为表层锌铝粉的活化阶段,中期为锌铝粉的电化学保护阶段,后期为阻挡层保护阶段。中间阶段的持续时间最长,证明涂层的主要防护机制是金属粉的电化学保护。极化曲线出现了明显的类钝化现象,根据单独锌粉涂层,以及锌铝粉涂层的对比发现,这种类钝化现象的产生与铝粉没有直接的关系;结合锌铝粉涂层在浸泡失效过程中的极化曲线分析,得出这种类钝化现象的产生主要是因为锌粉的腐蚀产物造成的。
通过在涂液中添加无毒缓蚀剂来提高涂层的防护性能,并且通过电化学阻抗谱、极化曲线分析,得出缓蚀剂的作用机制,通过三种不同缓蚀剂的对比,筛选最佳的缓蚀剂。结果表明在涂液中添加缓蚀剂,明显增加了涂层的腐蚀电阻,降低了腐蚀电流,从而降低了锌铝粉的消耗速率,使得涂层的阴极防护期延长。在三种环保型缓蚀剂中,涂液中添加磷钼酸钠(Na_3PO_4·12MoO_4)使得涂层腐蚀电阻最大,腐蚀电流最小,涂层的防护性能提高的最大。
因为本论文是在相关文献很少的基础上自行研制水性金属粉涂层,并从事性能分析、性能改进等方面的研究。整个研究需要深入涉及的内容较多,因此要使该技术应用于实际工业生产,还有许多内容需要进一步地深入和完善。
Since 21~(th) century, anticorrosive industry is confront with the pressure from both environment-protection and energy-conservation. Silane-base treatments can replace the traditional treatments with remarkable advantages in relation to environmental, safety and costs issues.
The Dacromet coating with high corrosion resistance technology was a popular metal anticorrosion technology for many metals. Its applications in some fields such as automobile industry were getting increasingly common because of the advantages of less pollution, excellent anticorrosion property and non-hydrogen embrittlement. Since the conventional Dacromet treatment agent contains hexavalent chromium ions, which are hazardous, adverse effects on the human body, and environmental contamination, due to the elution of chromium from protective films have been a serious concern. Furthermore, legal restrictions have been imposed in various countries on the use of hexavalent chromium even in rust inhibitors for metallic surfaces. In response to society’s need for new, environmentally compatible products, many research has endeavored to develop new coating systems that are environmentally friendly. In the countries such as Germany、America、Japan and Korea ,many kinds of non-chromate zinc/Aluminium coating have developed.
The objective of this thesis is to develop an environmentally benign coating,which does not utilize harmful chromium compounds and can be used for corrosion inhibition of a metal surface, comprising a slurry mixture in which coated zinc and aluminum fine powder treated with a hydrophilic coupling agent is suspended in an silane bonding solution. The optimal conditions were screened out..Since the coating hasn’t any chromium ,and free of any other toxic compounds, it has friendly environmental performance. And because it composed of a large number of metal flakes, the coating is conductive. As the pre–processing of the coating doesn’t have acid washing, the coating is hydrogen embrittlement free.
The appearance of coating was observed and studied through microscope, SEM, and EDS. The result showed that: the coating combined with metal substrates tightly, and the thickness of coating was uniform. Corrosion potential and electrochemical impedance spectroscopy ( EIS) measurement s were used to study the corrosion electrochemical behavior of the modified coatings immersed in 3.5% NaCl solution. The results indicated that the process of action of the coating during immersion presented three stages. At the initial stage, the flaked zinc powder on the surface layer of the coating started to activate due to the attack of the electrolyte. In the middle stage, the coating exhibited electrochemical protection for the substrate. For the third stage, the barrier protection of the coating predominated. The middle stage lasted a longer period than the third stage, suggesting a strong cathodic protection and a weak barrier mechanism of corrosion prevention of the silane zinc–aluminum coating.
Further more, in this thesis, we also study the corrosion properties of the coating with three different inhibiting blended in definite proportion. The results indicated that the addition of inhibitors can improve the protection performance of the coating, mitigating the consumption of the zinc and aluminium powder in the coating. Among the three inhibitors phosphomolybdate is the best, while the effect of cerium chloride is better than that of sodium molybdate.
In order to put this process into industrial use, there are still many problems waiting for further research and amelioration.
引文
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