大气污染物硫酸铵和氯化钠混合盐粒沉降对电路板铜大气腐蚀的加速机制

doi:10.11902/1005.4537.2021.138

中国腐蚀与防护学报

2022, Vol. 42

Issue (4): 540-550 DOI: 10.11902/1005.4537.2021.138

研究报告

本期目录 | 过刊浏览

大气污染物硫酸铵和氯化钠混合盐粒沉降对电路板铜大气腐蚀的加速机制

马小泽¹, 孟令东², 曹祥康¹, 肖松¹, 董泽华¹(

)

^1.华中科技大学化学与化工学院武汉 430074
^2.装甲兵学院材料学院北京 100086

Influence of Co-deposition of Pollutant Particulates Ammonium Sulfate and Sodium Chloride on Atmospheric Corrosion of Copper of Printed Circuit Board

MA Xiaoze¹, MENG Lingdong², CAO Xiangkang¹, XIAO Song¹, DONG Zehua¹(

)

^1.School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
^2.School of Materials, Academy of Armored Forces, Beijing 100086, China

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摘要:

采用电化学阻抗 (EIS)、石英晶体微天平 (QCM) 和铜箔电阻探针 (TER) 等多种大气腐蚀测量技术,以表面沉积不同比例 (NH₄)₂SO₄和NaCl混合盐粒下的电路板铜箔为样本,在气候试验箱中模拟研究了电路板铜在模拟污染大气环境下的初期大气腐蚀行为。结果表明：在30 ℃ RH90%环境中且表面沉积量相同时,在腐蚀初期 (<30 h),(NH₄)₂SO₄和NaCl混合盐粒对铜的腐蚀性比沉积单一NaCl盐粒的体系更强；但30 h后,情况发生反转,混合盐粒对铜的腐蚀相比单一NaCl盐粒体系反而显著降低,且当混合比例为1∶1时,(NH₄)₂SO₄对NaCl腐蚀的抑制作用最强 (抑制比达84%)。通过腐蚀产物的SEM、XRD、XPS分析可知,在腐蚀前期,由于NH₄⁺对Cu的腐蚀促进作用使铜表面快速形成了较为致密的Cu₂O腐蚀产物,从而显著减缓了铜基底腐蚀。尽管沉积NaCl盐粒的铜表面也生成了Cu₂O腐蚀产物,但相对比较疏松多孔,反而会因为腐蚀产物的阴极促进作用加速腐蚀产物层下的Cu腐蚀。

关键词 ：大气腐蚀, 电路板铜, 污染物, 腐蚀监测, 电阻探针, 石英晶体微天平

Abstract：

The initial atmospheric corrosion behavior of Cu foils induced by co-depositioned with of particulates with different proportions of (NH₄)₂SO₄ and NaCl particles in a weathering chamber was assessed via electrochemical impedance (EIS), quartz crystal microbalance (QCM) and thin foil electrical resistance probe (TER). The results show that the mixed salt particles of (NH₄)₂SO₄ and NaCl promote the initial atmospheric corrosion of PCB-Cu compared with sole NaCl salt particles in the initial 30 h when the total deposition amount is equal. However, after 30 h, the atmospheric corrosion rate of PCB-Cu beneath the mixed salts is significantly lower than that beneath the sole NaCl particles when the mixing ratio of (NH₄)₂SO₄ to NaCl is 1:1, and the inhibition ratio of Cu corrosion can reach 84%, indicating that the (NH₄)₂SO₄ can refrain the corrosion of PCB-Cu beneath induced by NaCl particles. According to the SEM, XRD and XPS analysis of corrosion products, in the early stage of corrosion, due to the catalytic effect of NH4⁺ on the corrosion of Cu, dense Cu₂O corrosion products quickly formed on the copper surface, which dramatically refrains the corrosion of Cu substrate. Although Cu₂O corrosion products are also generated on PCB-Cu surface where NaCl particles are deposited, they are relatively loose and porous, which could accelerate the corrosion of Cu beneath porous Cu₂O layer due to the cathodic depolarization of the corrosion product layer.

Key words： atmospheric corrosion PCB copper pollutant corrosion monitoring electrical resistance probe quartz crystal microbalance

收稿日期: 2021-06-15

ZTFLH:

TG174

基金资助:国家自然科学基金(51371087)

通讯作者: 董泽华 E-mail: zhdong@hust.edu.cn

Corresponding author: DONG Zehua E-mail: zhdong@hust.edu.cn

作者简介: 马小泽,男,1996年生,硕士生

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引用本文:

马小泽, 孟令东, 曹祥康, 肖松, 董泽华. 大气污染物硫酸铵和氯化钠混合盐粒沉降对电路板铜大气腐蚀的加速机制[J]. 中国腐蚀与防护学报, 2022, 42(4): 540-550.
Xiaoze MA, Lingdong MENG, Xiangkang CAO, Song XIAO, Zehua DONG. Influence of Co-deposition of Pollutant Particulates Ammonium Sulfate and Sodium Chloride on Atmospheric Corrosion of Copper of Printed Circuit Board. Journal of Chinese Society for Corrosion and protection, 2022, 42(4): 540-550.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.138 或 https://www.jcscp.org/CN/Y2022/V42/I4/540

图1 沉积不同比例混合盐粒的Cu梳齿电极在30 ℃下RH80%气候箱中暴露72 h后的EIS曲线

图2 对称铜梳齿电极在盐粒下的吸附薄液膜模型及相应的等效电路图

表1 沉积不同比例盐粒的梳齿铜电极在30 ℃,RH80%下暴露72 h后的EIS拟合结果

图3 沉积40 µg/cm2 (NH4)2SO4或NaCl盐粒的铜梳齿电极在30 ℃,不同RH条件下暴露2 h后的Bode图

图4 沉积不同比例混合盐粒的铜梳齿电极在30 ℃,RH90%气候箱中暴露72 h后的EIS曲线

表2 30 ℃,RH90%条件下表面沉积不同比例盐粒72 h时铜梳齿电极的EIS拟合结果

图5 沉积不同比例盐粒下铜梳齿电极在30 ℃,RH90%气候箱中暴露时低频阻抗随时间的变化

图6 沉积不同比例硫酸钠,硫酸铵和NaCl盐粒的铜梳齿电极在30 ℃,RH90%条件下暴露时的|Z|0.01 Hz对比图

图7 沉积不同比例盐粒的QCM镀铜晶片在30 ℃,RH 90%条件下暴露时的增重曲线

图8 在30 ℃和RH90%条件下暴露时Cu箔的厚度损失以及腐蚀速率随时间及盐粒比例的变化曲线

图9 表面沉积不同比例盐粒的铜片在30 ℃,RH90%条件下暴露72 h后的腐蚀产物XRD图

图10 沉积40 µg/cm2 NaCl,NaCl: (NH4)2SO4 (1:1),(NH4)2SO4的Cu在30 ℃和RH90%条件下暴露3 d后表面XPS谱图

图11 未沉积和沉积不同比例盐粒的铜试样在30 ℃和RH90%条件下暴露3 d后的微观腐蚀形貌

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