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金属学报  2019, Vol. 55 Issue (7): 840-848    DOI: 10.11900/0412.1961.2018.00558
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Mo元素及热处理对Ni2CrFeMox高熵合金在NaCl溶液中耐蚀性能的影响
魏琳1,王志军1(),吴庆峰1,尚旭亮2,李俊杰1,王锦程1
1. 西北工业大学凝固技术国家重点实验室 西安 710072
2. 中信戴卡股份有限公司 秦皇岛 066011
Effect of Mo Element and Heat Treatment on Corrosion Resistance of Ni2CrFeMox High-Entropy Alloyin NaCl Solution
Lin WEI1,Zhijun WANG1(),Qingfeng WU1,Xuliang SHANG2,Junjie LI1,Jincheng WANG1
1. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China
2. Citic Daika Co. , Ltd. , Qinhuangdao 066011, China
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摘要: 

利用循环极化曲线、激光共聚焦扫描显微镜(LSCM)、 SEM和 XPS等测试方法研究了Mo元素及热处理对Ni2CrFeMox高熵合金在3.5%NaCl (质量分数)溶液中耐蚀性能的影响。结果表明,铸态Ni2CrFeMox高熵合金的耐蚀性能明显高于316L不锈钢,其中Ni2CrFeMo0.2合金具有最小的维钝电流密度和腐蚀电流密度,耐蚀性能最好。过量Mo元素导致合金中析出σ相,发生电偶腐蚀,降低合金的耐蚀性能。固溶处理后,σ相的溶解及元素分布的均匀化减弱了电偶腐蚀的发生,耐蚀性能明显提高。

关键词 Mo元素高熵合金固溶处理耐蚀性能    
Abstract

As a new alloy design concept, the high-entropy alloy (HEA) and the formation of simple solid solution introduce excellent properties such as high hardness, high strength and corrosion resistance. Investigations have shown that the single solid solution CrCoFeNi alloy possesses good corrosion resistance. The addition of Mo is beneficial to the corrosion resistance of the HEAs for potential industrial applications in 3.5%NaCl (mass fraction) simulating seawater type environments. The major effect of Mo is to promote the pitting potential of the alloy and inhibit the dissolution of the passivation film by forming and retaining molybdenum oxyhydroxide or molybdates (MoO42-). Considering that the cost of pure Co is higher, Ni and Co elements have similar atomic size and valence electron concentration, and the corrosion resistance of pure Ni is higher than that of pure Co, Ni2CrFeMox HEA was designed by replacing Co element with Ni element in CoCrFeNiMox HEA. As the Mo content increases in the Ni2CrFeMox HEAs, the interdendrite is a Cr and Mo rich σ phase, and the dendrite is a Cr and Mo depleted fcc phase. The potential difference between interdendrites and dendrites leads to galvanic corrosion, which accelerates the localized corrosion of alloys. Here, a solution heat treatment process is selected to reduce the precipitation phase and improve the corrosion resistance of the alloy. The effects of Mo element and heat treatment on the corrosion resistance of Ni2CrFeMox HEA in 3.5%NaCl solution were tested. The results show that the corrosion resistance of as-cast Ni2CrFeMox HEA is obviously higher than that of 316L stainless steel. The Ni2CrFeMo0.2 alloy has the best corrosion resistance because of its minimum dimensional passive current density and corrosion current density. However, the addition of excessive Mo leads to the precipitation of σ phase and galvanic corrosion, which reduces the corrosion resistance of the alloy. After solution treatment, the uniformity of alloy structure and element distribution weakens galvanic corrosion, and the corrosion resistance is obviously improved.

Key wordsMo element    high entropy alloy    solution treatment    corrosion resistance
收稿日期: 2018-12-21     
ZTFLH:  TG132  
基金资助:国家自然科学基金项目(Nos.51471133);国家自然科学基金项目(51771149)
通讯作者: 王志军     E-mail: zhjwang@nwpu.edu.cn
Corresponding author: Zhijun WANG     E-mail: zhjwang@nwpu.edu.cn
作者简介: 魏 琳,女,1995年生,硕士

引用本文:

魏琳,王志军,吴庆峰,尚旭亮,李俊杰,王锦程. Mo元素及热处理对Ni2CrFeMox高熵合金在NaCl溶液中耐蚀性能的影响[J]. 金属学报, 2019, 55(7): 840-848.
Lin WEI, Zhijun WANG, Qingfeng WU, Xuliang SHANG, Junjie LI, Jincheng WANG. Effect of Mo Element and Heat Treatment on Corrosion Resistance of Ni2CrFeMox High-Entropy Alloyin NaCl Solution. Acta Metall Sin, 2019, 55(7): 840-848.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00558      或      https://www.ams.org.cn/CN/Y2019/V55/I7/840

图1  铸态Ni2CrFeMo
MaterialEcorr / mVicorr / (μA·cm-2)ipass / (μA·cm-2)Eb / mVEprot / mV
Ni2CrFeMo0.1-1352.13018.350986380
Ni2CrFeMo0.2-1790.8965.404920792
Ni2CrFeMo0.3-1031.95915.118896780
Ni2CrFeMo0.4-1211.71113.492954774
Ni2CrFeMo0.5-1252.01414.130966750
NiCoCrFeMo0.2[12]-1310.07216.000941747
316L-762.46322.135439-
表1  铸态Ni2CrFeMox合金和316L不锈钢在3.5%NaCl溶液中的电化学参数
图2  铸态Ni2CrFeMox合金和316L不锈钢在3.5%NaCl溶液中极化后的SEM像
图3  热处理态Ni2CrFeMox合金在3.5%NaCl溶液中的循环极化曲线
MaterialEcorr / mVicorr / (μA·cm-2)ipass / (μA·cm-2)Eb / mVEprot / mVErp / mV
Ni2CrFeMo0.1-1470.8017.302915802401
Ni2CrFeMo0.2-1830.3261.612952785497
Ni2CrFeMo0.3-2121.7458.548945780628
Ni2CrFeMo0.4-2361.8079.152890763382
Ni2CrFeMo0.5-2221.3238.810870744367
表2  热处理态Ni2CrFeMox合金在3.5%NaCl溶液中的电化学参数
图4  热处理态Ni2CrFeMox合金在3.5%NaCl溶液中极化后的SEM像
图5  铸态和热处理态Ni2FeCrMo0.2合金(未被极化腐蚀)的EDS面扫描图
图6  铸态 Ni2FeCrMox合金在3.5%NaCl溶液中的EIS
图7  铸态和热处理态Ni2FeCrMo0.2合金在3.5%NaCl溶液中的EIS
图8  铸态和热处理态Ni2CrFeMo0.2合金在3.5%NaCl溶液中恒电位+450 mV极化4 h后的XPS谱
ConditionCr(+3)/(0)Fe(+3)/(0)Mo(+6)/(+4)/(0)Ni(+2)/(0)
As-cast14.465.4661.29∶15.54∶23.170.46
Heat-treated17.991.5267.5∶15.18∶17.321.01
表3  铸态和热处理态Ni2CrFeMo0.2合金中各元素经XPS分析后不同氧化态之间的原子比
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