Cu-15Ni-8Sn合金在含S2- 的3.5%NaCl溶液中的腐蚀行为

doi:10.11902/1005.4537.2024.355

中国腐蚀与防护学报

2025, Vol. 45

Issue (5): 1408-1416 CSTR: 32134.14.1005.4537.2024.355 DOI: 10.11902/1005.4537.2024.355

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Cu-15Ni-8Sn合金在含S^2- 的3.5%NaCl溶液中的腐蚀行为

范世林¹^,², 杜娟²(

), 杨少丹³, 周延军⁴, 宋克兴², 张国赏², 岳鹏飞², 杨冉⁴, 王晓军¹

1 哈工大郑州研究院郑州 450046
2 河南省科学院材料研究所郑州 450046
3 郑州大学材料科学与工程学院郑州 450046
4 河南科技大学材料科学与工程学院洛阳 471023

Corrosion Behavior of Cu-15Ni-8Sn Alloy in 3.5%NaCl Solution Containing S^2-

FAN Shilin¹^,², DU Juan²(

), YANG Shaodan³, ZHOU Yanjun⁴, SONG Kexing², ZHANG Guoshang², YUE Pengfei², YANG Ran⁴, WANG Xiaojun¹

1 Zhengzhou Research Institute of Harbin Institute of Technology, Zhengzhou 450046, China
2 Institute of Materials Science, Henan Academy of Sciences, Zhengzhou 450046, China
3 School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450046, China
4 School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, China

引用本文:

范世林, 杜娟, 杨少丹, 周延军, 宋克兴, 张国赏, 岳鹏飞, 杨冉, 王晓军. Cu-15Ni-8Sn合金在含S^2- 的3.5%NaCl溶液中的腐蚀行为[J]. 中国腐蚀与防护学报, 2025, 45(5): 1408-1416.
Shilin FAN, Juan DU, Shaodan YANG, Yanjun ZHOU, Kexing SONG, Guoshang ZHANG, Pengfei YUE, Ran YANG, Xiaojun WANG. Corrosion Behavior of Cu-15Ni-8Sn Alloy in 3.5%NaCl Solution Containing S^2-[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1408-1416.

全文: PDF(12782 KB) HTML

摘要:

通过静态浸泡腐蚀实验，研究了Cu-15Ni-8Sn合金在含有10 mg/L S^2-条件下腐蚀时间对合金静态腐蚀行为的影响规律，并与不含S^2-的腐蚀行为进行对比。采用电化学阻抗谱(EIS)测试方法，结合扫描电子显微镜(SEM)、能谱分析(EDS)和X射线光电子能谱(XPS)等表征手段，探讨静态浸泡时间对合金电化学行为、腐蚀形貌的影响规律，揭示含/不含S^2-条件下合金腐蚀机理。结果表明，在不含S^2-的溶液中浸泡30 d后，Cu-15Ni-8Sn合金表面形成稳定的钝化膜，主要由碱式氯化铜Cu₂(OH)₃Cl组成，钝化膜能够有效阻止Cl⁻的进一步侵蚀，腐蚀速率为0.02235 g·m^-2·h^-1。而在含S^2-的溶液中，初期生成的硫化物(Cu₂S和CuS)提供一定的保护作用，浸泡1 d后的腐蚀速率仅为0.00962 g·m^-2·h^-1，远低于未添加S²⁻的溶液(0.05674 g·m^-2·h^-1)中。但随着时间的延长，合金浸泡腐蚀30 d后，在含有S^2-的溶液中的腐蚀失重率为0.03418 g·m^-2·h^-1，高于不含S^2-的溶液中的腐蚀失重率，腐蚀产物变为Cu₂(OH)₃Cl、CuSO₄、CuS、Ni(OH)₂和SnS₂的混合物。这些腐蚀产物的多孔和非保护性特性增加了腐蚀点，硫化物膜的劣化和破裂进一步加剧了腐蚀过程，使得合金在含S^2-溶液中的平均腐蚀速率高于不含S^2-溶液中的。

关键词 ： Cu-15Ni-8Sn合金, S^2-腐蚀, 腐蚀行为

Abstract：

The corrosion behavior of Cu-15Ni-8Sn alloy in 3.5%NaCl solution containing 10 mg/L sulfur ions (S^2-) was assessed by means of immersion tests, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The results show that after 30 d of immersion in 3.5%NaCl solution without sulfur ions, a stable passivation film is formed on the surface of Cu-15Ni-8Sn alloy, mainly composed of basic copper chloride Cu₂(OH)₃Cl. The passivation film can effectively prevent the further attack of Cl^-, and the average corrosion rate is 0.02235 g·m^-2·h^-1. In sulfur ion-containing solutions, the sulfides (Cu₂S and CuS) formed in the initial stage provide a certain degree of protection. However, with the extension of time, after the alloy is immersed and corroded for 30 days in the solution containing sulfur ions, the corrosion weight loss rate is 0.03418 g·m^-2·h^-1, which is higher than that in the solution without sulfur ions. the corrosion products are turn into the mixture of basic copper chloride (Cu₂(OH)₃Cl), copper sulfate (CuSO₄), copper sulfide (CuS), nickel hydroxide (Ni(OH)₂), and tin sulfide (SnS₂). This porous corrosion film provides much weaker protection for the alloys, and the deterioration and rupture of the sulfide film further aggravate the corrosion process, making the average corrosion rate of the alloy in the sulfur ion-containing environment higher than that in a sulfur ion-free environment.

Key words： Cu-15Ni-8Sn alloy sulfide-induced corrosion corrosion behavior

收稿日期: 2024-10-31 32134.14.1005.4537.2024.355

ZTFLH:

TG172.5

基金资助:河南省科学院科研启动经费(231817003);河南省自然科学基金(242300420030)

通讯作者: 杜娟，E-mail：juan_du@hnas.ac.cn，研究方向为材料腐蚀与防护

Corresponding author: DU Juan, E-mail: juan_du@hnas.ac.cn

作者简介: 范世林，男，2001年生，硕士生

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	王晓军
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https://www.jcscp.org/CN/10.11902/1005.4537.2024.355 或 https://www.jcscp.org/CN/Y2025/V45/I5/1408

图1 Cu-15Ni-8Sn合金浸泡在0和10 mg/L Na2S的3.5%NaCl溶液中30 d的腐蚀速率

图2 Cu-15Ni-8Sn合金在含不同浓度Na2S的3.5NaCl溶液中浸泡30 d内的Nyquist图及Bode图

图3 Cu-15Ni-8Sn合金在不同Na2S含量的3.5%NaCl溶液中浸泡时EIS拟合的等效电路图

表1 Cu-15Ni-8Sn合金在不添加Na2S的3.5%NaCl水溶液中浸泡不同时间后的EIS拟合参数

表2 Cu-15Ni-8Sn合金在含10 mg/L Na2S的3.5%NaCl水溶液中浸泡不同时间后的EIS拟合参数

图4 Cu-15Ni-8Sn合金浸泡在Na2S含量不同的3.5%NaCl溶液中浸泡不同时间后的表面微观形貌与成分

图5 Cu-15Ni-8Sn合金在不同含量Na2S的3.5%NaCl溶液中浸泡30 d的截面形貌和元素分布

图6 Cu-15Ni-8Sn合金在含0和10 mg/L Na2S的3.5% NaCl溶液中浸泡30 d后的XRD谱

图7 Cu-15Ni-8Sn合金在不同含量Na2S的3.5%NaCl溶液中浸泡30 d后的XPS全谱图

图8 Cu-15Ni-8Sn合金在不同含量Na2S的3.5%NaCl溶液中浸泡30 d后腐蚀产物XPS图谱

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