方波恒电位着色时间对不锈钢着色膜耐蚀性能的影响
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摘要
以方波电位着色法在不锈钢表面制备彩色膜,可获得较快的膜生长速率,现有的硫酸方波电位着色研究未涉及着色时间对彩色膜耐蚀性的影响。采用无铬硫酸体系对304不锈钢进行交流方波恒电位电化学着色,运用色差计、扫描电镜及能谱仪、腐蚀加速浸泡试验和交流阻抗测试等方法,重点研究了硫酸介质中交流方波着色时间对着色膜着色性能和膜耐腐蚀性能的影响。结果表明:在高低电位幅值分别为0 V和1 V的方波脉冲条件下,20～120 min的着色时间范围内,膜的厚度随着着色时间增加而增厚,呈现不同色彩;但膜的耐腐蚀性能随时间增加并不呈线性增加关系,着色时间超过80 min,着色膜耐腐蚀性能反而下降,这与膜的双层结构有关:当着色时间超过80 min后,膜层由微孔钝化膜单层结构转变为顶层覆盖岛状富铬氧化物层的双层膜结构,顶层膜小岛之间的缝隙导致膜的微观电化学非均匀性,从而使膜的耐腐蚀性能降低。
The 304 stainless steel was colored by square wave potential pulse polarization method in chromium-free H2 SO4 solution. The effects of coloring time on the coloring performance and corrosion resistance were researched by using colorimeter,scanning electron microscopy,X-ray energy dispersive spectrometer,accelerated corrosion test and electrochemical impedance spectroscopy. Results showed that when the lower potential( 0 V) and higher potential( 1 V) of the square wave were applied,respectively,the obtained colored film showed an increasing trend in thickness and different colors with the coloring time increasing from 20 min to 120 min. However,the corrosion resistance of the colored film did not increase linearly versus the increasing coloring time. When the coloring process exceeded 80 min,the corrosion resistance inversely decreased. This was related to the double-layer structure of the film. While exceeding 80 min coloring,the film changed from microporous single layer structure into double layer structure with covering by a top island-shaped Cr-rich oxide film. The irregular gaps between adjacent islands resulted in the inhomogeneous electrochemical heterogeneity characteristics of the film,leading to the degradation of the corrosion resistance.
The 304 stainless steel was colored by square wave potential pulse polarization method in chromium-free H2 SO4 solution. The effects of coloring time on the coloring performance and corrosion resistance were researched by using colorimeter,scanning electron microscopy,X-ray energy dispersive spectrometer,accelerated corrosion test and electrochemical impedance spectroscopy. Results showed that when the lower potential( 0 V) and higher potential( 1 V) of the square wave were applied,respectively,the obtained colored film showed an increasing trend in thickness and different colors with the coloring time increasing from 20 min to 120 min. However,the corrosion resistance of the colored film did not increase linearly versus the increasing coloring time. When the coloring process exceeded 80 min,the corrosion resistance inversely decreased. This was related to the double-layer structure of the film. While exceeding 80 min coloring,the film changed from microporous single layer structure into double layer structure with covering by a top island-shaped Cr-rich oxide film. The irregular gaps between adjacent islands resulted in the inhomogeneous electrochemical heterogeneity characteristics of the film,leading to the degradation of the corrosion resistance.
引文
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[15]周一扬,吴继民.不锈钢恒电位方波充电法着色[J].材料保护,1997,30(1):38.
[16]CONRRADO R,BOCCHI N,ROCHA-FILHO R C,et al.Corrosion resistance of colored films grown on stainless steel by the alternating potential pulse method[J].Electrochimica Acta,2003,48(17):2 417-2 424.
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[2]CHENG Z H,XUE Y Q,JU H B.Chemical coloring on stainless steel by ultrasonic irradiation.[J].Ultrasonics Sonochemistry,2018,40:558-566.
[3]JUNQUEIRA R M R,LOUREIRO C R O,ANDRADE MS,et al.The chemical and mechanical characteristics of thermally aged interference thin films on stainless steel[J].Surface and Coatings Technology,2009,203(13):1 908-1 912.
[4]王海人,王锐,王麒钧,等.一种碳钢着彩色不锈钢光干涉色的方法:104862754A[P].2015-08-26.
[5]张长松,武卫明,阎冬,等.不锈钢电化学着色的研究进展[J].电镀与精饰,2018,40(4):18-24.
[6]王锐.一种无铬不锈钢着色新工艺的探讨[D].武汉:湖北大学,2016:11-14.
[7]张俊喜,陈健,程胜松,等.不锈钢载波钝化着色膜的形成机理研究[J].中国腐蚀与防护学报,1999,19(3):167-172.
[8]张俊喜,魏增福,乔亦男,等.不锈钢着色的“绿色”工艺研究[J].腐蚀与防护,2004,25(1):13-16.
[9]FUJIMOTO S,TSUJINO K,SHIBATA T.Growth and properties of Cr-rich thick and porous oxide films on Type 304stainless steel formed by square wave potential pulse polarisation[J].Electrochimica Acta,2003,47(4):543-551.
[10]杨喜云,陈白珍,龚竹青.316不锈钢电化学着色工艺研究[J].腐蚀科学与防护技术,2009,21(3):330-332.
[11]刘忠宝.彩色不锈钢制备及性能研究[D].西安:西安电子科技大学,2009:9-13
[12]魏军胜,唐子龙,宋诗哲.碱性介质中304不锈钢交流调制电位着色工艺研究[J].表面技术,2007,36(5):43-45.
[13]方景礼,刘琴,韩克平,等.XPS和AES研究不锈钢上蓝紫色钼酸盐转化膜[J].电镀与环保,1995,15(3):21-23.
[14]王鸿建,李宁.不锈钢着色的发展方向:中国机械工程学会第三届全国表面工程大会论文集[C].厦门:[出版者不详],1996:24-26
[15]周一扬,吴继民.不锈钢恒电位方波充电法着色[J].材料保护,1997,30(1):38.
[16]CONRRADO R,BOCCHI N,ROCHA-FILHO R C,et al.Corrosion resistance of colored films grown on stainless steel by the alternating potential pulse method[J].Electrochimica Acta,2003,48(17):2 417-2 424.
[17]STOYCHEV D,STEFANOV P,NICOLOVA D,et al.Chemical composition and corrosion resistance of passive chromate films formed on stainless steels 316 L and 1.4301[J].Materials Chemistry&Physics,2002,73(2):252-258.