不锈钢化学转化膜耐蚀性能的研究
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摘要
化学着色法是制备不锈钢化学转化膜的主要方法。化学着色法的优点是着色工件的形状可以很复杂，而且得到的转化膜颜色均匀，但是较难控制的是颜色的重现性。目前对于化学着色法这方面的研究工作基本上是在INCO法的基础上进行一些改进，着色溶液的成分为：CrO_3 200～300g/L，H_2SO_4 250～500g/L，温度80～90℃。不锈钢浸在着色溶液中，表面就会被氧化形成铬、铁、镍的氧化物，颜色也随着表面膜厚度的改变而变化。着色过程中不锈钢的表面电位会随时间发生变化，转化膜呈现的颜色与着色电位差有一定的对应关系，控制一定的电位差可得到相应颜色的转化膜。化学转化膜比不锈钢基体具有更强的耐蚀性，不同颜色的转化膜耐蚀性能也不同，这和膜层的结构和元素含量分布有关。
本文在对其他研究者的研究结果进行综合和总结的基础上，主要进行了以下内容的研究：
(1) 用化学着色法，在CrO_3-H_2SO_4着色溶液中加入适当的添加剂，对1Cr18Ni9Ti不锈钢进行了表面着色处理研究。确定了化学转化膜耐蚀最优工艺：着色溶液CrO_3 250g/L、H_2SO_4 270ml/L、添加剂20g/L，着色温度50℃，时间30min。添加剂的加入加快了着色过程，使工艺温度降低了30～40℃。
(2) 测量了着色过程中不锈钢的电位—时间曲线，研究了添加剂浓度和温度对着色过程的影响。根据着色电位-时间曲线得到了多种颜色转化膜的电位差范围，确定了着色时间—转化膜电位差—转化膜颜色的对应关系。通过控制一定的电位差即可得到相应颜色的转化膜，提高了化学着色法工艺的色彩重现性。
(3) 采用动电位极化法研究不锈钢化学转化膜的电化学稳定性；用光电子能谱(XPS)分析法和辉光光谱(GDOES)分析法对金黄色和蓝色转化膜层进行元素和结构对比分析，对两者耐蚀性能的差异进行了研究。
(4) 利用扫描电镜(SEM)观察转化膜点蚀源和蚀坑形貌及用电子能谱进行元素成分分析；用X射线衍射仪(XRD)定性定量分析点腐蚀产物组成，对转化膜点腐蚀机理进行了初步的探讨和研究。本文在此基础上提出了不锈钢化学转化膜点腐蚀发展模型。
Preparation of colored stainless steel usually takes advantage of chemical colouring method, which is the mainly means to obtain colored film. The shape of materials can be very complicated and the coloring will be uniform by chemical colouring, which are merits of it. However, the colour recurring is difficult for chemical colouring. At present, all the study work on chemical colouring based on INCO method, and the component of colouring solutions are: CrO3 200~300g/L, H2SO4 250~500g/L, temperature 80~90℃. The oxide of Cr, Fe and Ni will be formed on stainless steel surface by colouring processes. The colour of film changed with thickness. The potential of stainless steel changed with time during colouring processes. There is correlative relation between the potential difference and colour of stainless steel. The correlative colored films can be obtained by controlling the correlative potential differences. The corrosion resistance of colored film is superior to stainless steel. Various colored film have di
fferent corrosion resistan.ce, which depends on the element distributes and configuration of film.
Based on some important results and conclusion from previous work, major content of this paper is listed as follows:
(1) Eperiment of chemical colouring of lCrl8Ni9Ti stainless steel with proper additives added to CrO3-H2SO4 colouring solution is studied. The colored film with the best corrosion resistance is obtained by colouring with the processes of CrO3 250g/L> H2SO4 270ml/L> proper additives 20g/L, colouring temperature 50℃, time 30min The results show that the addition of proper additives can improve the colouring speed and decrease colouring temperature 30~40℃.
(2) The potential-time curve during colouring measured, and the effect of amount of additives and time on colouring processes of stainless steel are discussed. The potential differences of several colored film with different colour are confirmed according to the potential-time curves, and the correlative relation between the potential difference and colour of stainless steel is discussed. The correlative colored films can be obtained by controlling the correlative potential differences, which improved the colour recurring of chemical colouring processes successfully.
(3) The electrochemistry stability of colored film is studied by potentiodynamic anodic plarization; The element distributes and configuration of yellow film and blue film are analysed by x-ray
photoelectron spectroscopy and glow discharge optical emission spectrometry, which discussed the difference of corrosion resistance of them.
(4) The pitting origins of colored film are characterized by SEM and electron spectroscopy and the composition of pitting products are confirmed and measured by XRD. The primary study on pitting mechanism of colored stainless steel and the model of pitting growth are initiated in this paper.
本文在对其他研究者的研究结果进行综合和总结的基础上，主要进行了以下内容的研究：
(1) 用化学着色法，在CrO_3-H_2SO_4着色溶液中加入适当的添加剂，对1Cr18Ni9Ti不锈钢进行了表面着色处理研究。确定了化学转化膜耐蚀最优工艺：着色溶液CrO_3 250g/L、H_2SO_4 270ml/L、添加剂20g/L，着色温度50℃，时间30min。添加剂的加入加快了着色过程，使工艺温度降低了30～40℃。
(2) 测量了着色过程中不锈钢的电位—时间曲线，研究了添加剂浓度和温度对着色过程的影响。根据着色电位-时间曲线得到了多种颜色转化膜的电位差范围，确定了着色时间—转化膜电位差—转化膜颜色的对应关系。通过控制一定的电位差即可得到相应颜色的转化膜，提高了化学着色法工艺的色彩重现性。
(3) 采用动电位极化法研究不锈钢化学转化膜的电化学稳定性；用光电子能谱(XPS)分析法和辉光光谱(GDOES)分析法对金黄色和蓝色转化膜层进行元素和结构对比分析，对两者耐蚀性能的差异进行了研究。
(4) 利用扫描电镜(SEM)观察转化膜点蚀源和蚀坑形貌及用电子能谱进行元素成分分析；用X射线衍射仪(XRD)定性定量分析点腐蚀产物组成，对转化膜点腐蚀机理进行了初步的探讨和研究。本文在此基础上提出了不锈钢化学转化膜点腐蚀发展模型。
Preparation of colored stainless steel usually takes advantage of chemical colouring method, which is the mainly means to obtain colored film. The shape of materials can be very complicated and the coloring will be uniform by chemical colouring, which are merits of it. However, the colour recurring is difficult for chemical colouring. At present, all the study work on chemical colouring based on INCO method, and the component of colouring solutions are: CrO3 200~300g/L, H2SO4 250~500g/L, temperature 80~90℃. The oxide of Cr, Fe and Ni will be formed on stainless steel surface by colouring processes. The colour of film changed with thickness. The potential of stainless steel changed with time during colouring processes. There is correlative relation between the potential difference and colour of stainless steel. The correlative colored films can be obtained by controlling the correlative potential differences. The corrosion resistance of colored film is superior to stainless steel. Various colored film have di
fferent corrosion resistan.ce, which depends on the element distributes and configuration of film.
Based on some important results and conclusion from previous work, major content of this paper is listed as follows:
(1) Eperiment of chemical colouring of lCrl8Ni9Ti stainless steel with proper additives added to CrO3-H2SO4 colouring solution is studied. The colored film with the best corrosion resistance is obtained by colouring with the processes of CrO3 250g/L> H2SO4 270ml/L> proper additives 20g/L, colouring temperature 50℃, time 30min The results show that the addition of proper additives can improve the colouring speed and decrease colouring temperature 30~40℃.
(2) The potential-time curve during colouring measured, and the effect of amount of additives and time on colouring processes of stainless steel are discussed. The potential differences of several colored film with different colour are confirmed according to the potential-time curves, and the correlative relation between the potential difference and colour of stainless steel is discussed. The correlative colored films can be obtained by controlling the correlative potential differences, which improved the colour recurring of chemical colouring processes successfully.
(3) The electrochemistry stability of colored film is studied by potentiodynamic anodic plarization; The element distributes and configuration of yellow film and blue film are analysed by x-ray
photoelectron spectroscopy and glow discharge optical emission spectrometry, which discussed the difference of corrosion resistance of them.
(4) The pitting origins of colored film are characterized by SEM and electron spectroscopy and the composition of pitting products are confirmed and measured by XRD. The primary study on pitting mechanism of colored stainless steel and the model of pitting growth are initiated in this paper.
引文
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[2] 李青。不锈钢着色工艺及彩色不锈钢的应用[J]．材料保护，1994，27(1)：1～6
[3] 王先友，蒋汉瀛。彩色不锈钢生产工艺及其耐蚀性的研究[J]．材料保护，1994，13(3)：5～8
[4] 周细应，万润根，韦金平等。不锈钢化学着色工艺探讨[J]．材料保护，1995，28(11)：14～15
[5] 张颖，陶珍东，马艳芳等。不锈钢着色研究[J]．腐蚀与防护，Vol．19，No．4，Aug．1998：175～177
[6] 王满力，周元康，黄威良。金属表面氧化色膜研究[J]。材料保护，2002，35(12)：39～40
[7] 周元康，王满力，罗述洁等 不锈钢着色的色泽控制[J]．材料保护，Vol．30，No．11，Nov．1997：20～22
[8] 倪小平。不锈钢着黑色工艺[J]．电镀与精饰，Vol．22，No．5，Sep．2000：31～33．
[9] 梅世云，周元康。不锈钢着色膜的耐磨性[J]．材料保护，Vol．33，No．11，Nov．2000：10～11
[10] 费敬银，秦熊浦，严卫东等。不锈钢表面处理技术的研究[J]．材料保护，Vol．33，No．11，No v．2000：45～46
[11] 张碧泉，卢兆忠，刘祖滨。304光亮不锈钢着色工艺研究[J]．电镀与环保，1997，17(2)：20～22
[12] 张碧泉，卢兆忠。不锈钢上黄绿色铬酸盐转化膜的研究[J]。电镀与涂饰，1998，17(4)：9～11
[13] 张碧泉，卢兆忠，林建民。不锈钢上紫红色铬酸盐转化膜的研究[J]。材料保护，1999，32(3)：27～28
[14] 郭稚弧，王海人，贾法龙。不锈钢着色新技术的研究[J]．材料保护，2000，33(5)：32～34
[15] 欧阳贵、左丹江、羊秋福。平扳不锈钢着色工艺[J]，材料保护，2003，36(1)：44～45
[16] J. S. Noh, N. J. Laycock, W. Gao. Effects of nitric acid passivation on the pitting resistance of 316 stainless steel[J]. Corrosion Science, 2000, 42:2069～2084
[17] Tarja Laitinen. Localized corrosion of stainless: steel in chloride, sulfate and thiosulfate containing environment[J]. Corrosion Science, 2000, 42:421～441
[18] N. J. Laycock, R. C. Newman. Localised dissolution kinetics, salt films and pitting
potentials[J]. Corrosion Science, 1997, 39(10-11): 1771～1790
[19] D. Wallinder, J. Pan, C. Leygraf. EIS and XPS study of surface modification of 316LVM stainless steel after passivation[J]. Corrosion Science, 1999, 41:275～289
[20] 刘烈炜，胡倩，郭砜．硫化氢对不锈钢表面钝化膜破坏研究[J]．中国腐蚀与防护学报，2002，22(1)：22～26
[21] M. Kaneko, H. S. Isaacs. Pitting of stainless steel in bromide, chloride and bromide/chloride solutions[J]. Corrosion Science, 2000, 42:67～78
[22] J. M. Bastidas, J. L. Polo, C. L. Torres. A study on the stability of AISI 316L stainless steel pitting corrosion through its transfer function[J]. Corrosion Science, 2001, 43:269～281
[23] F. Wenger, S. Cheriet, B. Talhi. Electrochemical impedance of pits. Influence of the pit morphology[J]. Corrosion Science, 1997, 39(7): 1239～1252
[24] T. Hong, M. Nagumo. Effect of surface roughness on early stages of pitting corrosion of type 301 stainless steel[J]. Corrosion SGience, 1997, 39(9): 1665～1672
[25] M. Fregoness, H. Idrissi, H. Mazille. Initiation and propagation steps in pitting corrosion of austenitic stainless steels: monitoring by acoustic emission[J]. Corrosion Science, 2001, 43: 627～641
[26] S. Virtanen, B. Surber, P. Nylund. Influence of MoO_4~(2-)anion in the electrolyte on passivity breakdown of iron[J]. Corrosion Science, 2001, 43:1165～1177
[27] G. O. Ilevbare, G. T. Burstein. The role of alloyed molybdenum in the inhibition of pitting corrosion in stainless steels[J]. 2001,43:485～513
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