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材料研究学报  2024, Vol. 38 Issue (3): 208-220    DOI: 10.11901/1005.3093.2023.254
  研究论文 本期目录 | 过刊浏览 |
冷喷涂Zn15Al合金涂层在NaCl溶液中的腐蚀行为和防护机制
徐龙1(), 李继文2, 崔传禹1, 卢祺1, 杨浩1, 赵聪聪1
1.季华实验室 材料科学与技术研究部 佛山 528200
2.中国科学院金属研究所 核用材料与安全评价重点实验室 沈阳 110016
Corrosion Behavior of Cold Sprayed Zn15Al Alloy Coating on Q235 Carbon Steel in NaCl Aqueous Solution
XU Long1(), LI Jiwen2, CUI Chuanyu1, LU Qi1, YANG Hao1, ZHAO Congcong1
1.Materials Science and Technology Research Department, Ji Hua Laboratory, Foshan 528200, China
2.Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
引用本文:

徐龙, 李继文, 崔传禹, 卢祺, 杨浩, 赵聪聪. 冷喷涂Zn15Al合金涂层在NaCl溶液中的腐蚀行为和防护机制[J]. 材料研究学报, 2024, 38(3): 208-220.
Long XU, Jiwen LI, Chuanyu CUI, Qi LU, Hao YANG, Congcong ZHAO. Corrosion Behavior of Cold Sprayed Zn15Al Alloy Coating on Q235 Carbon Steel in NaCl Aqueous Solution[J]. Chinese Journal of Materials Research, 2024, 38(3): 208-220.

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摘要: 

采用低压冷喷涂技术在Q235碳钢基材表面制备冷喷涂锌(CS-Zn)和锌铝合金涂层(CS-Zn15Al)，使用SEM观察、XRD谱、测量开路电位、电化学阻抗谱和动电位极化曲线等手段对其表征，研究了涂层在NaCl溶液中的腐蚀行为和腐蚀产物影响涂层防护性能的机制。结果表明，CS-Zn涂层在NaCl溶液中浸泡期内腐蚀严重，而CS-Zn15Al涂层的腐蚀速率较低，耐蚀性能较好。CS-Zn的主要腐蚀产物是ZnO，其多孔状的结构特点和半导体属性会破坏产物层的致密结构，降低电荷转移电阻，促进涂层腐蚀反应的发生；而添加Al元素能促进保护性腐蚀产物Zn5(OH)8Cl2·H2O和层状双氢氧化物Zn6Al2(OH)16CO3·4H2O的生成，显著提高对腐蚀介质的屏蔽。同时，添加Al降低了涂层的腐蚀电位、增强了对涂层的阴极保护作用，保护性腐蚀产物层的生成降低了腐蚀电流密度，延长了涂层的使用寿命。添加Al元素可实现涂层防护性能和耐久性的协同提高。
关键词 ： 材料失效与保护,  锌合金涂层,  电化学阻抗谱,  冷喷涂    
Abstract：

Cold-sprayed coatings Zn (CS-Zn) and Zn15Al alloy (CS-Zn15Al) were prepared on Q235 carbon steel plates via low-pressure cold spraying technique. The corrosion behavior of the coatings in 3.5% NaCl aqueous solution was assessed by means of electrochemical measurement of open circuit potential, electrochemical impedance and potentiodynamic polarization curves, as well as SEM with EDS, XRD. The results indicate that the CS-Zn coating undergoes severe corrosion during immersion, while the CS-Zn15Al coating corrodes at a slower rate and exhibits superior corrosion resistance. XRD results reveal that the dominant corrosion product of CS-Zn is ZnO, which possesses porous structural characteristics that disrupt the compactness of the corrosion product layer. Furthermore, its semiconductor properties decrease the charge transfer resistance, thereby accelerating the process of corrosion. In the contrast, as for CS-Zn15Al, the incorporation of Al facilitates the formation of protective corrosion products, namely Zn5(OH)8Cl2·H2O and layered double hydroxides Zn6Al2(OH)16CO3·4H2O. The shielding effect of CS-Zn15Al coating was significantly enhanced by this layer of corrosion products. Furthermore, electrochemical measurements demonstrate that the addition of Al reduces the corrosion potential of the coating, thereby enhancing its cathodic protection ability, and decreases the corrosion current density due to the generation of protective corrosion products. In conclusion, the addition of Al can synergistically enhance the anticorrosion performance and durability of the coating.
Key words： material failure and protection    zinc alloy coatings    electrochemical impedance spectroscopy    cold spraying
收稿日期: 2023-05-08     
ZTFLH:  TG174  
基金资助:广东省基础与应用基础研究基金(2020A1515110982)
通讯作者: 徐龙，xulong@jihualab.com，研究方向为海水腐蚀与防护涂层
Corresponding author: XU Long, Tel:17755333229, E-mail: xulong@jihualab.com
作者简介: 徐 龙，男，1992年生，博士
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https://www.cjmr.org/CN/10.11901/1005.3093.2023.254      或      https://www.cjmr.org/CN/Y2024/V38/I3/208

图1  Zn粉和Zn15Al合金粉形貌的二次电子像和背散射像以及Zn和Zn15Al粉体的粒径分布
SampleAlFeSiPbCdZn
Zn0.05210.02530.03950.00310.0029Bal.
Zn15Al14.7520.12510.08950.00310.0029Bal.
表1  Zn和Zn15Al合金粉的化学成分
ElementCMnSiSPFe
Content≤ 0.12≤ 0.50≤ 0.30≤ 0.04≤ 0.03Bal.
表2  Q235碳钢基材的化学成分
图2  CS-Zn涂层截面的形貌和元素分布
图3  CS-Zn15Al涂层截面的形貌和元素分布
图4  冷喷涂CS-Zn及CS-Zn15Al涂层的XRD谱
图5  涂层的开路电位和低频阻抗模值随浸泡时间的变化
图6  浸泡4416 h后CS-Zn涂层界面处的形貌和元素分布
图7  浸泡4416 h后CS-Zn15Al涂层界面处的形貌和元素分布
图8  浸泡4416 h后涂层腐蚀产物的物相分析
图9  浸泡后涂层的表层和内层腐蚀产物的形貌
Element1#2#3#4#5#
Zn63.268.164.660.762.2
O36.131.925.133.521.7
Cl0.7-10.33.415.4
Al---2.40.7
表3  不同位置对应元素EDS结果
图10  浸泡不同时间和表层产物去除后涂层的极化曲线
图11  不同浸泡时间极化曲线的腐蚀电流密度与腐蚀电位
图12  CS-Zn和CS-Zn15Al涂层的Nyquist图随浸泡时间的变化
图13  CS-Zn和CS-Zn15Al涂层的Bode图和相位角随浸泡时间的变化
图14  等效电路示意图
t/ hRs/ Ω·cm2CPE1 / S·s n ·cm-2n1Rc/ Ω·cm2CPE2 / S·s n ·cm-2n2Rct/ Ω·cm2CPE3n3RFe/ Ω·cm2ChiSq
13.41.37 × 10-20.42272.38.34 × 10-40.6943.1---8.16 × 10-4
723.57.54 × 10-40.4111353.38 × 10-40.7827.4---3.80 × 10-4
1443.66.44 × 10-40.6114692.20 × 10-40.8396.3---3.63 × 10-4
2403.81.13 × 10-30.3920122.92 × 10-40.76402.2---4.17 × 10-4
7203.52.64 × 10-40.8125509.46 × 10-40.581033---2.55 × 10-4
14404.11.23 × 10-50.6233035.37 × 10-40.86751.5---5.35 × 10-4
24004.82.53 × 10-30.6929543.68 × 10-30.72291.77.68 × 10-60.799.251.09 × 10-4
36484.72.76 × 10-30.7121981.53 × 10-30.7882.33.59 × 10-60.7713.931.23 × 10-4
44164.86.10 × 10-30.7414576.17 × 10-30.5745.12.33 × 10-50.5929.35.60 × 10-5
表4  CS-Zn涂层不同时间点的阻抗谱拟合结果
t/ hRs/ Ω·cm2CPE1 / S·s n ·cm-2n1Rc/ Ω·cm2CPE2 / S·s n ·cm-2n2Rct/ Ω·cm2WCPE3 / S·s n ·cm-2n3RFe/ Ω·cm2ChiSq
13.42.12 × 10-40.6814079.55 × 10-40.656552----9.32 × 10-4
724.61.97 × 10-40.77321.51.48 × 10-30.623405----3.95 × 10-4
1443.32.73 × 10-40.75452.61.49 × 10-30.712614----5.63 × 10-4
2403.72.52 × 10-40.75439.62.54 × 10-30.6515472.5 × 10-3---5.08 × 10-4
7203.92.86 × 10-40.6921702.09 × 10-30.6910301.7 × 10-3---6.81 × 10-4
14404.11.32 × 10-40.5814201.76 × 10-40.7533571.5 × 10-3---8.70 × 10-5
24004.12.07 × 10-40.42361.52.91 × 10-40.666165----5.19 × 10-4
36484.75.40 × 10-40.56680.31.37 × 10-40.915290----5.19 × 10-4
44163.94.98 × 10-40.59389.23.11 × 10-40.824511-1.90 × 10-40.4143.82.28 × 10-4
表5  CS-Zn15Al涂层不同时间点阻抗谱的拟合数据
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