正十六硫醇分子在Ag表面的自组装动力学及其保护作用

doi:10.11902/1005.4537.2019.023

中国腐蚀与防护学报

2020, Vol. 40

Issue (3): 281-288 DOI: 10.11902/1005.4537.2019.023

研究报告

本期目录 | 过刊浏览

正十六硫醇分子在Ag表面的自组装动力学及其保护作用

赵博儒¹, 孙志¹, 赵健伟²(

), 陈智栋¹(

)

1 常州大学材料科学与工程学院常州 213100
2 嘉兴学院材料与纺织工程学院嘉兴 314001

Self-assembly Process of Hexadecanethiol on Silver Plating Surface and Its Protectiveness

ZHAO Boru¹, SUN Zhi¹, ZHAO Jianwei²(

), CHEN Zhidong¹(

)

1 School of Materials Science and Engineering, Changzhou University, Changzhou 213100, China
2 College of Materials and Textile Engineering, Jiaxing University, Jiaxing 314001, China

全文: PDF(4193 KB) HTML

摘要:

利用充放电电容法、接触角测量法和电化学阻抗法研究了正十六硫醇在Ag镀层表面的自组装行为。在浓度为10和100 μmol·L^-1条件下，由充放电电容法得到吸附速率常数分别为 (1.3±0.2)×10⁶和 (2.8±0.5)×10⁴ mol^-1·L·s^-1，由接触角方法得到的吸附速率常数分别为 (9.3±0.7)×10⁵和 (3.4±0.6)×10⁴ mol^-1·L·s^-1，两种方法得到的结果一致。同时，结果也表明低浓度的硫醇分子有更高的吸附速率常数。Tafel极化曲线表明，经5 mmol·L^-1的正十六硫醇溶液浸泡15 min后，Ag镀件在阴极和阳极区域的电流密度显著降低，缓蚀率可达98.6%。80 °C下烘烤12 h实验、Na₂S溶液腐蚀实验以及H₂S气体腐蚀实验的结果进一步证实上述保护工艺既符合生产操作要求，又可以获得显著的耐蚀效果。

关键词 ：十六硫醇, 自组装, 电银镀, 腐蚀

Abstract：

The self-assembly process of hexadecanethiol on the surface of Ag-plating on Cu-plate has been studied by means of charge and discharge capacitance method, contact angle measurement, and electrochemical impedance spectroscopy. The theoretical fitting to the capacitance data acquired from tests in 10 and 100 μmol·L^-1 solution gives the adsorption rate constants of (1.3±0.2)×10⁶ and (2.8±0.5)×10⁴ mol^-1·L·s^-1 respectively, which are closed to those of (9.3±0.7)×10⁵ and (3.4±0.6)×10⁴ mol^-1·L·s^-1 obtained by using contact angle measurements. The results indicate that the adsorption rate constant of hexadecanethiol in the dilute solution is higher than that in the concentrated one. Tafel polarization curves reveal that both anodic and cathodic currents are significantly reduced while the silver plating was immersed in 5 mmol·L^-1 hexadecanethiol solution for 15 min, correspondingly the corrosion inhibition rate reaches 98.6%. Furthermore, when the Ag-plating was firstly covered with a self-assembled film through immersion in 5 mmol·L^-1 hexadecanethiol solution and then subjected to post heat treatment at 80 ℃ for 12 h, as expected, the treated Ag-plating exhibits excellent corrosion resistance to Na₂S solution and H₂S containing atmosphere. Therefore, the application of hexadecanethiol solution is effective and feasible in practice.

Key words： hexadecanethiol self-assembly silver plating corrosion

收稿日期: 2019-02-13

ZTFLH:

TG172.3

基金资助:浙江省自然科学基金(LY19B030006);浙江省自然科学基金(LY19E090005)

通讯作者: 赵健伟,陈智栋 E-mail: jwzhao@mail.zjxu.edu.cn;zdchen@cczu.edu.cn

Corresponding author: ZHAO Jianwei,CHEN Zhidong E-mail: jwzhao@mail.zjxu.edu.cn;zdchen@cczu.edu.cn

作者简介: 赵博儒，男，1993年生，硕士生

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引用本文:

赵博儒, 孙志, 赵健伟, 陈智栋. 正十六硫醇分子在Ag表面的自组装动力学及其保护作用[J]. 中国腐蚀与防护学报, 2020, 40(3): 281-288.
Boru ZHAO, Zhi SUN, Jianwei ZHAO, Zhidong CHEN. Self-assembly Process of Hexadecanethiol on Silver Plating Surface and Its Protectiveness. Journal of Chinese Society for Corrosion and protection, 2020, 40(3): 281-288.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2019.023 或 https://www.jcscp.org/CN/Y2020/V40/I3/281

图1 银镀件在100 μmol·L-1的C16H33SH溶液中浸泡不同时间后在0.15 mol·L-1的KNO3溶液中的循环伏安曲线及不同浓度硫醇浸泡下覆盖度随时间的变化关系

图2 不同硫醇浓度条件下银镀层的接触角测试值和理论模拟值随自组装时间的变化

图3 银镀件在含100 μmol·L-1 C16H33SH的溶液中浸泡不同时间后在0.15 mol·L-1的KNO3溶液中的电化学阻抗谱图

图4 银镀件在3个高浓度的C16H33SH溶液中浸泡15 min后在3.5%NaCl溶液中的Tafel极化曲线

表1 由Tafel曲线得到的腐蚀参数

图5 含不同浓度C16H33SH溶液未处理与处理的银镀件高温烘烤后的宏观形貌图

图6 在不同浓度C16H33SH溶液中处理的银镀件在0.1 mol·L-1 Na2S溶液中浸泡不同时间后的显微照片

图7 在不同浓度C16H33SH溶液中处理的银镀件经H2S气体腐蚀后的形貌图

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