杨元成,王友彬,赵晋玮,周佳顺,冯济强,高峰,韦悦周.腐蚀产物中Zn5(OH)8Cl2对纯Zn腐蚀行为的影响[J].表面技术,2024,53(4):98-109, 151.
YANG Yuancheng,WANG Youbin,ZHAO Jinwei,ZHOU Jiashun,FENG Jiqiang,GAO Feng,WEI Yuezhou.Effect of Zn5(OH)8Cl2 in Corrosion Products on Corrosion Behaviour of Pure Zn[J].Surface Technology,2024,53(4):98-109, 151 |
| 腐蚀产物中Zn5(OH)8Cl2对纯Zn腐蚀行为的影响 |
| Effect of Zn5(OH)8Cl2 in Corrosion Products on Corrosion Behaviour of Pure Zn |
| 投稿时间：2022-12-08 修订日期：2023-05-06 |
| DOI：10.16490/j.cnki.issn.1001-3660.2024.04.009 |
| 中文关键词: 腐蚀产物 Zn5(OH)8Cl2 纯Zn 原位生长 腐蚀防护 |
| 英文关键词:corrosion products Zn5(OH)8Cl2 pure Zn in-situ growth corrosion protection |
| 基金项目:广西自然科学基金面上项目(2021GXNSFAA196046);国家自然科学基金(11975082) |
| 作者 | 单位 |
| 杨元成 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 王友彬 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 赵晋玮 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 周佳顺 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 冯济强 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 高峰 | 广西大学 省部共建特色金属材料与组合结构全寿命安全国家重点实验室 资源环境与材料学院，南宁 530004 |
| 韦悦周 | 南华大学 核科学技术学院，湖南 衡阳 421001 |
|
| Author | Institution |
| YANG Yuancheng | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| WANG Youbin | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| ZHAO Jinwei | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| ZHOU Jiashun | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| FENG Jiqiang | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| GAO Feng | State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China |
| WEI Yuezhou | School of Nuclear Science and Technology, University of South China, Hunan Hengyang 421001, China |
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| 中文摘要: |
| 目的 探究纯Zn腐蚀产物中碱式氯化锌(Zn5(OH)8Cl2，ZHC)对其腐蚀防护性能的影响以及腐蚀防护机理。方法 通过原位生长法在纯Zn表面制备一层ZHC膜。通过X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)，分析了样品的物相组成和微观形貌。通过电化学阻抗谱(EIS)和动电位极化曲线(Tafel)，评估了ZHC膜对纯Zn腐蚀防护性能的影响。结果 纯Zn表面先形成了一层致密细小的ZHC纳米片，铺满整个纯Zn表面后，在第一层ZHC上形成第二层较大尺寸的ZHC纳米片。预制备的ZHC膜可以使纯Zn的腐蚀电流密度从78.23 μA/cm2降低到2.08 μA/cm2，腐蚀电位从‒1.050 V(vs. SCE)提升到‒0.998 V(vs. SCE)，并且随着ZHC制备时间的增加，阴极斜率(βc)逐渐增大，这表明ZHC可以有效阻碍电荷转移，抑制阴极的氧还原，减缓纯Zn的腐蚀速率，对Zn基体的腐蚀起到防护作用。在浸泡腐蚀过程中，ZHC可以抑制HZ的生成，减少絮状腐蚀产物的生成。在短期浸泡过程中，纯Zn的阻抗值随着预制备ZHC的增加而逐渐增大，这是因为生成的腐蚀产物填补ZHC纳米片的空隙，使腐蚀产物膜致密，ZHC膜对Zn基体能起到较好的防护作用。在长期浸泡过程中，ZHC/Zn的阻抗值下降，这是因为ZHC膜破裂，提供了新的腐蚀通道，导致ZHC膜对纯Zn的防护作用下降。结论 ZHC膜可以减缓纯Zn的腐蚀速率。对比纯Zn和ZHC/Zn在浸泡过程中的腐蚀行为可知，在短期浸泡过程中，随着预制备ZHC的增加，对纯Zn的防护性能逐渐提高;在长期浸泡腐蚀过程中，ZHC膜对纯Zn腐蚀的防护作用逐渐下降。 |
| 英文摘要: |
| The effect of the complex corrosion product film on the corrosion resistance of Zn has been studied by many researchers in recent years. However, the effect of certain corrosion product on the corrosion resistance of substrate has not been explained clearly. Simonkolleite (Zn5(OH)8Cl2, ZHC) is one of the corrosion products of Zn and its alloys. Most researchers believe that the corrosion product film containing ZHC can improve the anti-corrosion performance of the substrate, but the impact of ZHC on the anti-corrosion performance of the substrate is not very detailed. Therefore, this work aims to explore the effect of the ZHC on the corrosion protection performance of pure Zn, and the corrosion protection mechanism of ZHC film on pure Zn. The ZHC film was prepared on the surface of pure Zn by in-situ growth method. The phase and microstructure of the corrosion products on the surface of specimens were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The effect of ZHC on the corrosion protection performance of pure Zn was analyzed with potentiodynamic polarization curve (Tafel) and electrochemical impedance spectroscopy (EIS). It was found that the dense and fine layer of ZHC nanoflakes was formed on the surface of pure Zn, covering the entire surface of pure Zn. Then, the second layer of large size ZHC nanosheets was formed on the first layer of ZHC. The results of the polarization curve showed that the ZHC could reduce the corrosion current density of pure Zn from 78.23 μA/cm2 to 2.08 μA/cm2, and make the corrosion potential move to the positive potential from ‒1.050 V (vs. SCE) to ‒0.998 V (vs. SCE), and with the increase of preparation time, cathode slope (βc) gradually increased, which indicated that ZHC could effectively hinder the charge transfer, inhibit the cathodic oxygen reduction, slow down the corrosion rate of pure Zn and provide corrosion protection for pure Zn. The results of the XRD and SEM showed that the ZHC could inhibit the formation of the corrosion product hydrozincite (Zn5(CO3)2(OH)6, HZ) and reduce the formation of flocculent corrosion products in the immersion corrosion process. During the short-term immersion, the impedance value of pure Zn gradually increased with the pre-prepared ZHC, which was due to the fact that the generated corrosion products filled the gaps in the ZHC nanosheets, making the corrosion product film dense and effectively hindering the contact between the corrosion medium and pure Zn, and the ZHC film could provide better protection for the Zn substrate. During the long-term immersion process, the impedance value of ZHC/Zn decreased, due to the cracks of the ZHC film, providing a new corrosion channel and leading to a decrease in the protective effect of the ZHC film on pure Zn. To sum up, ZHC film can slow down the corrosion rate of pure Zn. Through comparison between the corrosion behavior of pure Zn and ZHC/Zn during immersion corrosion, in the early stage of immersion, it can be seen that the corrosion protection performance of pure Zn increases with the increasing amount of ZHC. In the long-term immersion, it can be seen that the corrosion protection effect of ZHC film on pure Zn gradually decreases. |
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