锌基材料的环保型无铬钝化剂研究
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摘要
钢铁镀锌后通常要对其表面的锌进行钝化处理,在传统工艺中,通常采用六价铬作为钝化成膜剂,这是因为铬酸盐钝化膜有许多优点,例如工艺简单、成本低、钝化膜的耐蚀性高,钝化膜在受到损伤后可以自我修复,另外,铬酸盐钝化膜通常呈彩虹色因而具有一定的装饰作用。然而由于六价铬酸盐具有很强的毒性,可使人体的某些器官癌变,并对或环境造成很大的危害,因此许多发达国家纷纷立法禁止六价铬相关工艺的应用及产品的生产和流通。
本文的主要内容是研究并采用无毒环保型钝化剂来提高镀锌板的耐蚀性,希望可以找到取代传统六价铬钝化工艺的方法。实验所采用的钝化剂包括了无机和有机两大类,其中无机体系重点研究了铝酸盐、钛酸盐和稀土铈盐三种钝化剂；有机体系选择了KH-792、KH-560、KH-570、BTSE这四种有机硅烷作为钝化剂；实验还研究了无机钝化剂与有机硅烷之间的复合钝化作用。结果发现,在无机钝化剂中,稀土钝化效果相对较好,而有机无机复合是提高钝化膜耐蚀性的有效途径之一,实验最后还提出了一种表达钝化膜自修复性能优劣的方法,即“自修复效率”,并据此研究比较了多种钝化膜自修复性能的大小。本论文的主要工作主要有如下几点：
(1)研究了在钼酸盐体系中,磷酸根的存在与否对钝化膜耐蚀性的影响,并将磷酸根的作用与硫酸根、硝酸根进行了对比,实验发现磷酸可与钼酸形成磷钼杂多酸,这种酸在钝化膜中所成的难溶盐对耐蚀性的提高有较大作用,而其它类型的酸根则不具有这一功能。另外,实验还研究了一些有机添加剂如单宁酸、植酸与钼酸盐的协同钝化作用,它们也能在一定程度上提高钼酸盐体系钝化膜的耐蚀性,另外,由于有机添加剂的加入使得钝化膜的颜色有所改变,因而可以提高钝化膜的装饰性。实验最后还探讨了磷钼酸盐钝化的机理。
(2)研究比较了在钛盐体系中,三氯化钛、四氯化钛、硫酸氧钛和硫酸钛作为钛盐体系钝化剂的优缺点,并研究了钛盐钝化工艺中,钝化液各组分所起的作用以及钝化工艺操作条件的影响,以及钛盐钝化的机理。结果发现,采用成本相对较低廉的硫酸钛同样可以达到与硫酸氧钛和三氯化钛同样的钝化效果,且其钝化效果优于钼酸盐体系。
(3)研究了两种截然不同的稀土铈盐钝化工艺,一种采用常规的酸性溶液进行快速钝化,钝化时间为1min左右；而另一种采用中性溶液进行缓慢钝化,钝化时间需要一个星期。结果发现,酸性快速钝化所获得的钝化膜的耐蚀性不及铬酸盐钝化膜；中性缓慢钝化所获得的钝化膜的耐蚀性虽然优于铬酸盐钝化膜,但处理时间过长,不宜工业化应用。另外,在不影响钝化膜耐蚀性的前提下,本文研究了几种方法来缩短钝化时间,发现暴气钝化法有一定的作用。
(4)研究了上述四种有机硅烷在与无机钝化剂复合前后所形成的钝化膜的形貌及耐蚀性的变化,并分析了复合钝化的机理及有机无机各组分的作用。实验发现,上述四种有机硅烷与钼酸盐、钛酸盐或铈盐复合后,钝化膜的耐蚀性有一定程度的提高,提高的程度与有机硅烷种类、无机钝化剂的特性以及两者之间的配比有较大关系。
(5)研究和评价了无铬钝化膜和传统铬酸盐钝化膜自修复作用发生的机理,并提出了一个新概念：“自修复效率”,用它能够比较钝化膜自修复作用的大小。实验还研究了几种有代表性的钝化膜的自修复效率,并将其与铬酸盐钝化膜进行了比较。结果发现,目前实验所得到的所有种类的钝化膜的自修复效率均大大低于铬酸盐钝化膜。
Zinc or zinc alloy coatings on steels applied by electrodeposition or hot dipping are wildly used to give protections for steels. The passivation process of zinc is a usual treatment for the galvanized steels. In conventional practice, a very popular way to reduce the corrosion rate of zinc was the use of chemical conversion layers based on hexavalent chromium ions, which can increase the passivation tendency of the zinc. This procedure is quite effective also for improving the adhesion of organic coatings deposited on the zinc surface, but there is a serious environmental problem associated with the use of Cr6+ in the formation of chromate conversion films for galvanized steels because of the high toxicity and the strong carcinogensis of the Cr6+ ions. So it is necessary to investigate alternative methods for corrosion protection for the use of chromium salts, which are now restricted by environmental protection legislation all over the world.
In this paper, environmentally friendly chromate-free conversion coatings will be developed on zinc surface in comparison with traditional chromate treatments. Molybdate, titanium salt and cerium salt were selected as inorganic passivators, and silane coupling agents (SCA) include KH-792, KH-560, KH-570 and BTSE were selected as organic passivators. What is more, compound passivation between organic and inorganic passivators was investigated. The results showed that the cerium based conversion film was relatively better than molybdate or titanium based conversion film, and the compound effect between organic and inorganic passivators could increase the corrosion resistance to some extent. Finally, a new conception, "self-healing efficiency" was proposed to evaluate the self-healing abilities of films. Here are the main works we done.
(1) Molybdate passivation system was investigated. The effect of the phosphate radical, sulfate radical or nitrate radical in conversion solution were studied, and the result showed that molybdophosphoric heteropoly acid was formed by phosphoric acid and molybdate, yet sulfate radical or nitrate radical exhibit no such performance. Moreover, some additives such as tannic acid or phytic acid were confirmed that they can increase the corrosion resistance as well as the ornament of the passivation films. Finally, the mechanism of the forming of molybdophosphoric heteropoly film was discussed.
(2) As a kind of inorganic passivator, titanium trichloride, titanium tetrachloride, titanyl sulfate and titanium sulfate were investigated, and the contributions of each constituent in conversion solution were stuied. The result showed that the conversion film formed on zinc by the relatively cheap titanium sulfate was no less than titanium trichloride or titanyl sulfate, and generally, conversion coatings form by titanium salt exceeded that of molybdate.
(3) Two kinds of quite different cerium based passivation methods were applied to form conversion coatings on zinc, one is carried out in an acidic conversion solution with a very fast passivation procedure less than 1 min, the other is carried out in a neutral conversion solution with a very long passivation procedure more than 1 week. The result showed that the conversion film formed in the acidic solution compare unfavourably with the one formed in the neutral solution. However, the passivation time of the latter method is too long to be applied industrially. Several feasible solutions to this problem therefore were studied to reduce the passivation time, and aeration was found to be a relatively better method.
(4) In this part, silane coupling agents were used as passivators, and four kinds of SCA include KH-792, KH-560, KH-570 and BTSE were investigated befor and after they compound with three kinds of inorganic passivators include molybdate, titanium salt and cerium salt. The compound effect between SCA and inorganic passivators changed the microstructural aspects of the films, and in the meantime, increased the corrosion resistance of the conversion films. But which worth the whistle is that the corrosion resistance of the film raised by the compound effect depends largely on the sort of SCA and inorganic passivators as well as the mixture ratio between them.
(5) The self healing ability of chromium include and chromium free conversion coating was investigated, and a new conception, "self-healing efficiency" was proposed to evaluate the self-healing abilities of films. The result showed that the self-healing efficiency of all chromium free conversion coating was far below the conventional Cr6+ conversion film.
本文的主要内容是研究并采用无毒环保型钝化剂来提高镀锌板的耐蚀性,希望可以找到取代传统六价铬钝化工艺的方法。实验所采用的钝化剂包括了无机和有机两大类,其中无机体系重点研究了铝酸盐、钛酸盐和稀土铈盐三种钝化剂；有机体系选择了KH-792、KH-560、KH-570、BTSE这四种有机硅烷作为钝化剂；实验还研究了无机钝化剂与有机硅烷之间的复合钝化作用。结果发现,在无机钝化剂中,稀土钝化效果相对较好,而有机无机复合是提高钝化膜耐蚀性的有效途径之一,实验最后还提出了一种表达钝化膜自修复性能优劣的方法,即“自修复效率”,并据此研究比较了多种钝化膜自修复性能的大小。本论文的主要工作主要有如下几点：
(1)研究了在钼酸盐体系中,磷酸根的存在与否对钝化膜耐蚀性的影响,并将磷酸根的作用与硫酸根、硝酸根进行了对比,实验发现磷酸可与钼酸形成磷钼杂多酸,这种酸在钝化膜中所成的难溶盐对耐蚀性的提高有较大作用,而其它类型的酸根则不具有这一功能。另外,实验还研究了一些有机添加剂如单宁酸、植酸与钼酸盐的协同钝化作用,它们也能在一定程度上提高钼酸盐体系钝化膜的耐蚀性,另外,由于有机添加剂的加入使得钝化膜的颜色有所改变,因而可以提高钝化膜的装饰性。实验最后还探讨了磷钼酸盐钝化的机理。
(2)研究比较了在钛盐体系中,三氯化钛、四氯化钛、硫酸氧钛和硫酸钛作为钛盐体系钝化剂的优缺点,并研究了钛盐钝化工艺中,钝化液各组分所起的作用以及钝化工艺操作条件的影响,以及钛盐钝化的机理。结果发现,采用成本相对较低廉的硫酸钛同样可以达到与硫酸氧钛和三氯化钛同样的钝化效果,且其钝化效果优于钼酸盐体系。
(3)研究了两种截然不同的稀土铈盐钝化工艺,一种采用常规的酸性溶液进行快速钝化,钝化时间为1min左右；而另一种采用中性溶液进行缓慢钝化,钝化时间需要一个星期。结果发现,酸性快速钝化所获得的钝化膜的耐蚀性不及铬酸盐钝化膜；中性缓慢钝化所获得的钝化膜的耐蚀性虽然优于铬酸盐钝化膜,但处理时间过长,不宜工业化应用。另外,在不影响钝化膜耐蚀性的前提下,本文研究了几种方法来缩短钝化时间,发现暴气钝化法有一定的作用。
(4)研究了上述四种有机硅烷在与无机钝化剂复合前后所形成的钝化膜的形貌及耐蚀性的变化,并分析了复合钝化的机理及有机无机各组分的作用。实验发现,上述四种有机硅烷与钼酸盐、钛酸盐或铈盐复合后,钝化膜的耐蚀性有一定程度的提高,提高的程度与有机硅烷种类、无机钝化剂的特性以及两者之间的配比有较大关系。
(5)研究和评价了无铬钝化膜和传统铬酸盐钝化膜自修复作用发生的机理,并提出了一个新概念：“自修复效率”,用它能够比较钝化膜自修复作用的大小。实验还研究了几种有代表性的钝化膜的自修复效率,并将其与铬酸盐钝化膜进行了比较。结果发现,目前实验所得到的所有种类的钝化膜的自修复效率均大大低于铬酸盐钝化膜。
Zinc or zinc alloy coatings on steels applied by electrodeposition or hot dipping are wildly used to give protections for steels. The passivation process of zinc is a usual treatment for the galvanized steels. In conventional practice, a very popular way to reduce the corrosion rate of zinc was the use of chemical conversion layers based on hexavalent chromium ions, which can increase the passivation tendency of the zinc. This procedure is quite effective also for improving the adhesion of organic coatings deposited on the zinc surface, but there is a serious environmental problem associated with the use of Cr6+ in the formation of chromate conversion films for galvanized steels because of the high toxicity and the strong carcinogensis of the Cr6+ ions. So it is necessary to investigate alternative methods for corrosion protection for the use of chromium salts, which are now restricted by environmental protection legislation all over the world.
In this paper, environmentally friendly chromate-free conversion coatings will be developed on zinc surface in comparison with traditional chromate treatments. Molybdate, titanium salt and cerium salt were selected as inorganic passivators, and silane coupling agents (SCA) include KH-792, KH-560, KH-570 and BTSE were selected as organic passivators. What is more, compound passivation between organic and inorganic passivators was investigated. The results showed that the cerium based conversion film was relatively better than molybdate or titanium based conversion film, and the compound effect between organic and inorganic passivators could increase the corrosion resistance to some extent. Finally, a new conception, "self-healing efficiency" was proposed to evaluate the self-healing abilities of films. Here are the main works we done.
(1) Molybdate passivation system was investigated. The effect of the phosphate radical, sulfate radical or nitrate radical in conversion solution were studied, and the result showed that molybdophosphoric heteropoly acid was formed by phosphoric acid and molybdate, yet sulfate radical or nitrate radical exhibit no such performance. Moreover, some additives such as tannic acid or phytic acid were confirmed that they can increase the corrosion resistance as well as the ornament of the passivation films. Finally, the mechanism of the forming of molybdophosphoric heteropoly film was discussed.
(2) As a kind of inorganic passivator, titanium trichloride, titanium tetrachloride, titanyl sulfate and titanium sulfate were investigated, and the contributions of each constituent in conversion solution were stuied. The result showed that the conversion film formed on zinc by the relatively cheap titanium sulfate was no less than titanium trichloride or titanyl sulfate, and generally, conversion coatings form by titanium salt exceeded that of molybdate.
(3) Two kinds of quite different cerium based passivation methods were applied to form conversion coatings on zinc, one is carried out in an acidic conversion solution with a very fast passivation procedure less than 1 min, the other is carried out in a neutral conversion solution with a very long passivation procedure more than 1 week. The result showed that the conversion film formed in the acidic solution compare unfavourably with the one formed in the neutral solution. However, the passivation time of the latter method is too long to be applied industrially. Several feasible solutions to this problem therefore were studied to reduce the passivation time, and aeration was found to be a relatively better method.
(4) In this part, silane coupling agents were used as passivators, and four kinds of SCA include KH-792, KH-560, KH-570 and BTSE were investigated befor and after they compound with three kinds of inorganic passivators include molybdate, titanium salt and cerium salt. The compound effect between SCA and inorganic passivators changed the microstructural aspects of the films, and in the meantime, increased the corrosion resistance of the conversion films. But which worth the whistle is that the corrosion resistance of the film raised by the compound effect depends largely on the sort of SCA and inorganic passivators as well as the mixture ratio between them.
(5) The self healing ability of chromium include and chromium free conversion coating was investigated, and a new conception, "self-healing efficiency" was proposed to evaluate the self-healing abilities of films. The result showed that the self-healing efficiency of all chromium free conversion coating was far below the conventional Cr6+ conversion film.
引文
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