电镀锡板表面Cr2O3 钝化膜结构及耐蚀性演化的电化学阻抗谱研究

doi:10.11902/1005.4537.2025.185

中国腐蚀与防护学报

2026, Vol. 46

Issue (3): 756-766 CSTR: 32134.14.1005.4537.2025.185 DOI: 10.11902/1005.4537.2025.185

研究报告

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电镀锡板表面Cr₂O₃ 钝化膜结构及耐蚀性演化的电化学阻抗谱研究

刘状¹, 乔创², 姜金利³, 车欣¹(

), 代春丽⁴, 沈勇⁴, 郝龙²(

)

^1.沈阳工业大学材料科学与工程学院沈阳 110870
^2.中国科学院金属研究所材料腐蚀与防护中心沈阳 110016
^3.凌源钢铁股份有限公司凌源 122500
^4.中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Structure- and Corrosion Resistance-evolution of Cr₂O₃ Passivation Film on Tinplate Surface in Neutral NaCl- and Acidic NaCl + Na₂SO₃-solution

LIU Zhuang¹, QIAO Chuang², JIANG Jinli³, CHE Xin¹(

), DAI Chunli⁴, SHEN Yong⁴, HAO Long²(

)

^1.School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China
^2.Materials Corrosion and Protection Center, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^3.Lingyuan Iron and Steel Co. Ltd., Lingyuan 122500, China
^4.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

刘状, 乔创, 姜金利, 车欣, 代春丽, 沈勇, 郝龙. 电镀锡板表面Cr₂O₃ 钝化膜结构及耐蚀性演化的电化学阻抗谱研究[J]. 中国腐蚀与防护学报, 2026, 46(3): 756-766.
Zhuang LIU, Chuang QIAO, Jinli JIANG, Xin CHE, Chunli DAI, Yong SHEN, Long HAO. Structure- and Corrosion Resistance-evolution of Cr₂O₃ Passivation Film on Tinplate Surface in Neutral NaCl- and Acidic NaCl + Na₂SO₃-solution[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(3): 756-766.

全文: PDF(4583 KB) HTML

摘要:

随着电镀锡钢板表面镀锡量降低，其在储存运输过程中的腐蚀问题也逐渐凸显。而表面钝化膜结构及耐蚀性变化直接影响电镀锡板的腐蚀特性。本文采用电化学阻抗谱(EIS)方法，结合X射线光电子能谱(XPS)表征，研究了电镀锡板表面钝化膜结构及其在中性NaCl溶液与酸性NaCl + Na₂SO₃溶液中的耐蚀性随腐蚀时间的演化过程。结果表明，EIS方法可以用于研究电镀锡板表面钝化膜结构表征及其在腐蚀介质中的耐蚀性演化过程。镀锡板表面钝化膜呈现“双层结构”特征，外层富Cr、Sn氧化物，内层富Sn氧化物。镀锡板在NaCl溶液中的EIS响应表现为两个时间常数特征，分别对应于表面钝化膜的双层结构；但在NaCl + Na₂SO₃溶液中观察到的低频域和高频域两个时间常数，分别源自双电层和镀锡板表面残存膜层/新生成的产物层。电镀锡板在NaCl溶液中的耐蚀性较高，表面钝化膜层厚度随腐蚀时长变化并不显著，但在NaCl + Na₂SO₃溶液中，表面钝化膜层却迅速减薄，耐蚀性急剧降低。显然，镀锡钢板钝化膜在酸性溶液中的溶解是耐蚀性降低的主要原因。

关键词 ：电镀锡板, Cr₂O₃钝化膜层, EIS, 耐蚀性, 膜层结构

Abstract：

With the continuous improvement of the tin plating process for cold rolled steel plates, the amount of tin deposition on the tinplate surface has decreased in contrast to the traditional ones. This will directly affect the quality of the surface passivation film formed after the subsequent passivation treatment. Hence, it has been observed currently that corrosion troubles gradually occur during storage and transportation of tin-coated plates. Clearly, changes in the structure and corrosion characteristics of the surface passivation film will determine the corrosion behavior of the tinplate. Herein, the surface structure- and the corrosion performance-evolution of the surface passivation film on the tinplate in neutral NaCl solution and acidic NaCl + Na₂SO₃ solution was assessed by means of electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The results indicate that the as-received surface passivation film presents characteristics of "double-layered structure" with an outer layer rich in Cr and Sn oxides, while the inner layer is rich in Sn oxides. In addition, the EIS response of the tinplate in NaCl solution exhibits two time-constants characteristics, corresponding to the bi-layered structure of the passivation film. But the observed two time-constants locating at the low-frequency domain and high-frequency domain in NaCl + Na₂SO₃ solution are derived from the residual film layer/newly formed corrosion product layer and from the double layer at electrolyte/tinplate interface, respectively. Furthermore, the corrosion resistance of tinplate in NaCl solution is relatively high, and the surface passivation film thickness remains basically unchanged. However, in NaCl + Na₂SO₃ solution, the surface passivation film rapidly dissolves and thus the corrosion resistance decreases sharply. Therefore, the passivation film dissolution in acidic environment is the main reason for its reduced corrosion resistance. It follows that the EIS technique can effectively characterize and elucidate the structure of the passivation film on the tinplate surface and the evolution mechanism of its corrosion.

Key words： tinplate Cr₂O₃passivation film EIS corrosion resistance film structure

收稿日期: 2025-06-17 32134.14.1005.4537.2025.185

ZTFLH:

TG172

基金资助:国家自然科学基金(52401126);辽宁省自然科学基金(2025-BS-0164)

通讯作者: 郝龙，E-mail：lhao@imr.ac.cn，研究方向为腐蚀电化学阻抗谱技术及应用电化学;
车欣，E-mail：xiaoxin2004068@163.com，研究方向为轻金属结构材料组织与性能

Corresponding author: HAO Long, E-mail: lhao@imr.ac.cn;
CHE Xin, E-mail: xiaoxin2004068@163.com

作者简介: 刘状，男，1993年生，博士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.185 或 https://www.jcscp.org/CN/Y2026/V46/I3/756

图1 循环EIS测试方案示意图[25]

图2 原始态电镀锡板表面钝化膜成分和结构表征

图3 电镀锡板在不同腐蚀溶液浸泡过程中的EIS数据演化

图4 电镀锡板在不同腐蚀溶液浸泡过程中的OCP和|Z|0.01 Hz演化结果

图5 对EIS数据进行溶液电阻校正和复容抗转换后的结果

图6 拟合不同腐蚀溶液中电镀锡板EIS曲线使用的等效电路

表1 拟合图3a中EIS数据得到的电化学参数

图7 在不同腐蚀溶液浸泡过程中电镀锡板表面钝化膜厚度的演化

表2 拟合图3b中EIS数据得到的电化学参数

图8 电镀锡板在中性NaCl溶液中浸泡10 h后表面膜层的XPS精细谱

图9 电镀锡板在酸性NaCl + Na2SO3溶液中浸泡10 h后表面膜层的XPS精细谱

表3 电镀锡板样品在不同腐蚀溶液中浸泡后表面膜层的XPS分峰结果[31,34,35]

图10 反映电镀锡板表面钝化膜主要成分稳定性的电位E-pH图

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