腐蚀产物对锌合金镀层切边腐蚀行为的影响

doi:10.11902/1005.4537.2025.225

中国腐蚀与防护学报 DOI: 10.11902/1005.4537.2025.225

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腐蚀产物对锌合金镀层切边腐蚀行为的影响

李永坤¹,王友彬¹,周佳顺¹,高锋¹,王欣鹏²,汤宏群³

1. 广西大学
2. 广西大学资源环境与材料学院
3. 广西大学材料科学与工程学院

nfluence of corrosion products on the corrosion behavior of cut edges of zinc alloy coatings

引用本文:

李永坤王友彬周佳顺高锋王欣鹏汤宏群. 腐蚀产物对锌合金镀层切边腐蚀行为的影响[J]. 中国腐蚀与防护学报, 10.11902/1005.4537.2025.225.

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摘要: 目的基于腐蚀产物的防护性能探究锌基共晶合金镀层切边腐蚀行为。方法本工作选取纯Zn，以及Zn-3Mg、Zn-5Al和Zn-4Al-3Mg三种锌基共晶合金镀层作为研究对象，通过浸泡实验和盐雾试验的方法，采用扫描电镜（SEM）、能谱仪(EDS)、X射线衍射技术（XRD）等技术分析切边处腐蚀产物物相组成及形貌，采用扫描电化学显微镜（SECM）表征了不同共晶合金镀层切边的微区腐蚀行为。结果通过SEM和EDS分析腐蚀产物在切边处的镀层和靠近镀层的钢基体上均有分布，Zn和Zn-3Mg镀层镀层上的腐蚀产物主要为碱式氯化锌（Zn5(OH)8Cl2，ZHC），钢基体上的腐蚀产物主要为ZHC和碱式碳酸锌(Zn5(OH)6(CO3)2·H2O, HZ)；Zn-5Al和Zn-4Al-3Mg镀层其腐蚀产物还存在锌铝层状双金属氢氧化物 (Zn6Al2(OH)16CO3·4H2O, LDH)。SECM表明实验初期Zn-Al镀层与Zn-Al-Mg镀层的反馈电流相较于Zn镀层高，一段时间后Zn-Al镀层与Zn-Al-Mg镀层的反馈电流低于Zn镀层，在镀层表面和远离镀层一侧的钢基体表面的反馈电流较大，靠近镀层一侧的钢基体表面反馈电流较小，且整体反馈电流和电流凹陷随腐蚀时间而降低。盐雾腐蚀试验显示纯Zn镀层、Zn-Mg镀层、Zn-Al镀层与Zn-Al-Mg镀层切边样品的平均失重速率分别为1.04×10?2、9.88×10?3、5.73×10?3与5.21×10?3 g m?1 h?1。结论 Zn-4Al-3Mg镀层的切边耐腐蚀性最好，Zn-4Al-3Mg镀层的腐蚀产物层结构致密，保护性产物ZHC、LDH的含量较高，起到了协同防护作用，腐蚀产物层良好的防护性能使得Zn-Al-Mg镀层表现出较优的长久耐蚀性能。

关键词 ：锌基共晶合金, 腐蚀产物, 切边腐蚀, 微区腐蚀, 微区电化学, 腐蚀行为

Abstract：The steel is susceptible to atmospheric corrosion, zinc-based eutectic alloy coating with high corrosion resistance and sacrificial anode protection performance is widely used for corrosion protection of the steel. During use, zinc alloy-coated steel often requires cutting, which exposes the cut edges of the steel substrate to environmental corrosion, as these areas lack the protective coating. The corrosion resistance of zinc-based coatings is closely linked to the protective characteristics of the resulting corrosion products. This article studies influence of corrosion products on the cut-edge corrosion of zinc-based eutectic alloys. Pure Zn , Zn-3Mg, Zn-5Al, and Zn-4Al-3Mg alloys were selected as the coating for the steel substrate by hot-dip coating. The hot dip coating samples were cut into cylindrical samples and sealed using epoxy resin, leaving only one cut edge surface, and the cut edge surface was polished.The samples were subjected to immersion experiments in 5% NaCl solution. The microstructure of the samples was observed by a field emission scanning electron microscope (FE-SEM, Hitachi SU8020) equipped with an energy dispersive spectrometer (EDS, Oxford Aztec X-Max) system. The distribution of the corrosion products at the cut edges was observed by 3D microscope(LEICA DVM6).Scanning electrochemical microscope (SECM) measurements were conducted using feedback mode in a SECM system (CHI 920D).The working height (tip-substrate distance) was 20 μm to prevent the tip bumping into corrosion products. The tip was biased at +0.45 V vs. The test was performed using a salt spray corrosion chamber (Hengzi YFX-150) using the NSS neutral salt spray test standard. According to the national standard to calculate the weight loss analysis of the sample after the salt spray corrosion test . The physical composition of the corrosion products after salt spray corrosion was analyzed by X-ray diffraction (XRD, Rigaku SmartLab SE). The corrosion products on the Zn and Zn-3Mg coatings were mainly simonkolleite (Zn5(OH)8Cl2·H2O, ZHC) , and on the steel substrate were mainly ZHC and hydrozincite (Zn5(OH)6(CO3)2, HZ) ;For Zn-5Al and Zn-4Al-3Mg coatings, the main corrosion product was layered double hydroxide (Zn6Al2(OH)16CO3·4H2O, LDH)、ZHC and HZ. SECM showed that initially, the feedback currents of Zn-Al and Zn-Al-Mg coatings were higher than those of Zn. Over time, the feedback currents of Zn-Al and Zn-Al-Mg coatings decreased to levels below those of Zn, the feedback current on the surface of the coating and the surface of the steel substrate far away from the side of the coating is larger, the feedback current on the surface of the steel substrate close to the side of the coating is smaller, and the overall feedback current and current depression decrease with the corrosion time.Salt spray corrosion tests showed that the average weight loss rates of pure Zn plating, Zn-Mg plating, Zn-Al plating and Zn-Al-Mg plating cut edge samples were 1.04×10-2, 9.88×10-3, 5.73×10-3 and 5.21×10-3 g m-1 h-1. The cut edge corrosion resistance of Zn-4Al-3Mg coating is the best, the corrosion product layer of Zn-4Al-3Mg coating has a dense structure, and the higher content of protective products ZHC and LDH plays a synergistic protective effect, and the good protective performance of the corrosion product layer makes the Zn-Al-Mg coating show superior long-term corrosion resistance.

Key words： Zinc-based eutectic alloys Corrosion products Cutting edge corrosion Localized corrosion localized electrochemistry corrosion behavior

收稿日期: 2025-07-15

ZTFLH:

TG174.44

基金资助:国家自然科学基金;广西科技重大专项;广西科技重大专项;中国博士后科学基金

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