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中国腐蚀与防护学报  2022, Vol. 42 Issue (2): 218-226    DOI: 10.11902/1005.4537.2021.080
  研究报告 本期目录 | 过刊浏览 |
FeCrMn1.3NiAlx高熵合金显微组织演变及电化学钝化行为
张恒康, 黄峰(), 徐云峰, 袁玮, 邱耀, 刘静
武汉科技大学 省部共建耐火材料与冶金国家重点实验室 武汉 430081
Microstructure Evolution and Electrochemical Passivation Behavior of FeCrMn1.3NiAlx High Entropy Alloys
ZHANG Hengkang, HUANG Feng(), XU Yunfeng, YUAN Wei, QIU Yao, LIU Jing
State Key Laboratory of Refractory Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
全文: PDF(11595 KB)   HTML
摘要: 

采用真空电磁悬浮法熔炼了4种不同Al含量的FeCrMn1.3NiAlx (x=0,0.25,0.5,0.75) 高熵合金,通过FE-SEM、XRD、SKPFM、EPMA和动电位极化等方法研究了Al含量对铸态FeCrMn1.3NiAlx高熵合金显微组织及其在0.5 mol/L H2SO4溶液中钝化行为的影响规律及机理。结果表明:FeCrMn1.3NiAlx (x=0,0.25) 合金试样由fcc (Fe-Mn-Ni)+bcc (Fe-Cr-Mn) 结构组成,bcc结构的Fe-Cr-Mn相电化学活性较大而优先溶解,从而表现出两个明显的致钝电位和致钝电流峰;随着Al的添加,当x=0.5时,合金中fcc结构已基本消失,形成了颗粒和条带状的b2相 (Al-Ni-Mn) 均匀分布在具有bcc结构的Fe-Cr-Mn相上,因二者微区相电化学活性相差不大,仅呈现出一个融合的致钝电位和致钝电流峰,同时合金中新形成的硬质ρ相因具有较高的电化学活性,而呈现出低的致钝电位和较小的致钝电流密度;当x=0.75时,ρ相消失,对应的低致钝电位峰也随之消失。Al添加通过改变FeCrMn1.3NiAlx高熵合金中微区相组成、显微组织和电化学活性,从而影响其在0.5 mol/L H2SO4溶液中的电化学钝化行为,随着Al含量增加,合金致钝电流密度增加,产生的b2相钝化性能较差,使得合金的钝化性能降低。

关键词 高熵合金显微组织恒电位极化钝化行为    
Abstract

Four high entropy alloys of FeCrMn1.3NiAlx (x= 0, 0.25, 0.5, 0.75) with different Al content were smelted by vacuum magnetic suspension method. The effect of Al content on the microstructure and passivation behavior of the as-cast alloys FeCrMn1.3NiAlx in 0.5 mol/L H2SO4 solution was investigated by means of XRD, FE-SEM, SKPFM, EPMA and potentiodynamic polarization technique. The results show that the FeCrMn1.3NiAlx (x=0, 0.25) alloy presents a two-phase microstructure of fcc (Fe-Mn-Ni)+bcc (Fe-Cr-Mn). The Fe-Cr-Mn phase of bcc structure has higher electrochemical activity, and therewith is preferred to dissolve, which results in two obvious passivation-potential and -current peaks. As the Al addition reaches x=0.5, the fcc phase almost entirely disappeared in the alloy, therefore the alloy composed of the bcc Fe-Cr-Mn phase with uniformly distributed particles and strips of b2 phase (Al-Ni-Mn). Due to the difference in electrochemical activity of the above two phases is not much, so that, the alloy present only one passivation potential and passivation current peak. Meanwhile the new hard ρ-phase of higher electrochemical activity emerges in the alloy, which resulted in lower passivation potential and smaller passivation current density. The ρ-phase disappears for the alloy with x=0.75 Al, correspondingly, the low passivation potential peak also disappears. The addition of Al can affect the passivation behavior of FeCrMn1.3NiAlx high entropy alloys in 0.5 mol/L H2SO4 solution by changing the microstructure, composition and distribution of phases in local-areas, so as the electrochemical activity of FeCrMn1.3NiAlx high entropy alloys. With the increase of Al, the passivation current density of the alloy increases due to the poor passivation performance of b2 phase, which in turn reduces the passivation performance of the alloys.

Key wordshigh entropy alloy    microstructure    potentiostatic polarization    passivation behavior
收稿日期: 2021-04-16     
ZTFLH:  TG174  
基金资助:湖北省自然科学基金重点项目 (科技创新群体)(2021CFA023)
通讯作者: 黄峰     E-mail: huangfeng@wust.edu.cn
Corresponding author: HUANG Feng     E-mail: huangfeng@wust.edu.cn
作者简介: 张恒康,男,1998年生,硕士生

引用本文:

张恒康, 黄峰, 徐云峰, 袁玮, 邱耀, 刘静. FeCrMn1.3NiAlx高熵合金显微组织演变及电化学钝化行为[J]. 中国腐蚀与防护学报, 2022, 42(2): 218-226.
Hengkang ZHANG, Feng HUANG, Yunfeng XU, Wei YUAN, Yao QIU, Jing LIU. Microstructure Evolution and Electrochemical Passivation Behavior of FeCrMn1.3NiAlx High Entropy Alloys. Journal of Chinese Society for Corrosion and protection, 2022, 42(2): 218-226.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.080      或      https://www.jcscp.org/CN/Y2022/V42/I2/218

图1  FeCrMn1.3NiAlx合金的XRD谱
图2  FeCrMn1.3NiAlx合金的FE-SEM下的背散射电子图像
图3  FeCrMn1.3NiAlx合金各元素的FE-EPMA图谱
AlloyfccbccOther
Al0Fe-Mn-NiFe-Cr-Mn
Al0.25Fe-Mn-NiFe-Cr-Mn
Al0.5

Fe-Cr-Mn

Al-Ni-Mn (b2 phase)

Fe6Cr5Mn8 (ρ phase)
Al0.75

Fe-Cr-Mn

Al-Ni-Mn (b2 phase)

表1  FeCrMn1.3NiAlx合金各相中的主要元素成分
图4  FeCrMn1.3NiAlx合金的SKPFM形貌和Volta电位图
图5  FeCrMn1.3NiAlx合金在0.5 mol/L H2SO4溶液中的极化曲线
图6  FeCrMn1.3NiAlx合金在0.5 mol/L H2SO4致钝电位附近的放大图
AlloyPassivation current density / A·cm-2Passivation potential VMaintaining passivity current density / A·cm-2EcorrVIcorrA·cm-2
Al01#0.008-0.2301.6×10-4-0.3951.06×10-3
2#0.005-0.170
Al0.251#0.027-0.2412.1×10-5-0.4164.02×10-3
2#0.019-0.165
Al0.51#0.009-0.4095.9×10-5-0.4614.15×10-3
2#0.089-0.115
Al0.751#0.100-0.0943.2×10-5-0.4684.16×10-3
表2  FeCrMn1.3NiAlx高熵合金极化曲线中钝化参数
图7  FeCrMn1.3NiAlx合金恒电位极化后的三维组织形貌
1 Yeh J W, Chen S K, Lin S J. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes [J]. Adv. Eng. Mater., 2004, 6: 299
2 Yeh J W, Lin S J, Chin T S, et al. Formation of simple crystal structures in Cu-Co-Ni-Cr-Al-Fe-Ti-V alloys with multiprincipal metallic elements [J]. Metall. Mater. Trans., 2004, 35A: 2533
3 Zhang S, Wu C L, Zhang C H, et al. Laser surface alloying of FeCoCrAlNi high-entropy alloy on 304 stainless steel to enhance corrosion and cavitation erosion resistance [J]. Opt. Laser Technol., 2016, 84: 23
4 He J Y, Wang H, Huang H L, et al. A precipitation-hardened high-entropy alloy with outstanding tensile properties [J]. Acta Mater., 2016, 102: 187
5 Munitz A, Meshi L, Kaufman M J. Heat treatments' effects on the microstructure and mechanical properties of an equiatomic Al-Cr-Fe-Mn-Ni high entropy alloy [J]. Mater. Sci. Eng., 2017, 689A: 384
6 Hu Y T, Dong P F, Jiang L, et al. Corrosion behavior of riveted joints of TC4 Ti-alloy and 316L stainless steel in simulated marine atmosphere [J]. J. Chin. Soc. Corros. Prot., 2020, 40: 167
6 胡玉婷, 董鹏飞, 蒋立等. 海洋大气环境下TC4钛合金与316L不锈钢铆接件腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2020, 40: 167
7 Zhang H, Du N, Zhou W J, et al. Effect of Fe3+ on pitting corrosion of stainless steel in simulated seawater [J]. J. Chin. Soc. Corros. Prot., 2020, 40: 517
7 张浩, 杜楠, 周文杰等. 模拟海水溶液中Fe3+对不锈钢点蚀的影响 [J]. 中国腐蚀与防护学报, 2020, 40: 517
8 Sun J L, Zou D, Jin J, et al. Localized corrosion resistance of three commonly-used stainless steels [J]. Chin. J. Mater. Res., 2017, 31: 665
8 孙京丽, 邹丹, 金晶等. 三种常用不锈钢的耐局部腐蚀性能 [J]. 材料研究学报, 2017, 31: 665
9 Zhang W R, Liaw P K, Zhang Y. Science and technology in high-entropy alloys [J]. Sci. China Mater., 2018, 61: 2
10 Qiu Y, Thomas S, Gibson M A, et al. Corrosion of high entropy alloys [J]. npj Mater. Degrad., 2017, 1: 15
11 Massoud T, Maurice V, Klein L H, et al. Intergranular effects on the local electronic properties of the passive film on nickel [J]. Corros. Sci., 2013, 69: 245
12 Bettini E, Kivisäkk U, Leygraf C, et al. Study of corrosion behavior of a 2507 super duplex stainless steel: Influence of quenched-in and isothermal nitrides [J]. Int. J. Electrochem. Sci., 2013, 9: 61
13 Luo H, Li Z M, Mingers A M, et al. Corrosion behavior of an equiatomic CoCrFeMnNi high-entropy alloy compared with 304 stainless steel in sulfuric acid solution [J]. Corros. Sci., 2018, 134: 131
14 Lee C P, Chang C C, Chen Y Y, et al. Effect of the aluminium content of AlxCrFe1.5MnNi0.5 high-entropy alloys on the corrosion behaviour in aqueous environments [J]. Corros. Sci., 2008, 50: 2053
15 Zhang X, Cui H Z, Wang M L, et al. Effect of Al content on microstructure and corrosion resistance of AlxCoCrFeNi high entropy alloys [J]. Trans. Mater. Heat Treat., 2018, 39(12): 29
15 张雪, 崔洪芝, 王明亮等. Al含量对AlxCoCrFeNi系高熵合金组织和耐蚀性能的影响 [J]. 材料热处理学报, 2018, 39(12): 29
16 Li B Y, Peng K, Hu A P, et al. Structure and properties of FeCoNiCrCu0.5Alx high-entropy alloy [J]. Trans. Nonferrous Met. Soc. China, 2013, 23: 735
17 Wang Y, Li M Y, Sun L L, et al. Microstructure and corrosion property of FeCrNiCo (Cu/Mn) high entropy alloys [J]. Chin. J. Nonferrous Met., 2020, 30(1): 94
17 王勇, 李明宇, 孙丽丽等. FeCrNiCo(Cu/Mn) 高熵合金组织及腐蚀性能 [J]. 中国有色金属学报, 2020, 30(1): 94
18 Chen S T, Tang W Y, Kuo Y F, et al. Microstructure and properties of age-hardenable AlxCrFe1.5MnNi0.5 alloys [J]. Mater. Sci. Eng., 2010, 527A: 5818
19 Zhang W W, Li R B. Study of microstructure and mechanical properties of FeNiMnCr0.75Alx high-entropy alloys [J]. Nonferrous Met. Mater. Eng., 2018, 39(3): 18
19 张威威, 李荣斌. 多主元FeNiMnCr0.75Alx高熵合金微观结构和力学性能的研究 [J]. 有色金属材料与工程, 2018, 39(3): 18
20 He J Y, Liu W H, Wang H, et al. Effects of Al addition on structural evolution and tensile properties of the FeCoNiCrMn high-entropy alloy system [J]. Acta Mater., 2014, 62: 105
21 Sathirachinda N, Pettersson R, Wessman S, et al. Study of nobility of chromium nitrides in isothermally aged duplex stainless steels by using SKPFM and SEM/EDS [J]. Corros. Sci., 2010, 52: 179
22 Kao Y F, Lee T D, Chen S K, et al. Electrochemical passive properties of AlxCoCrFeNi (x=0, 0.25, 0.50, 1.00) alloys in sulfuric acids [J]. Corros. Sci., 2010, 52: 1026
23 Wang Y, Cheng X Q, Li X G. Electrochemical behavior and compositions of passive films formed on the constituent phases of duplex stainless steel without coupling [J]. Electrochem. Commun., 2015, 57: 56
24 Tsai W T, Chen J R. Galvanic corrosion between the constituent phases in duplex stainless steel [J]. Corros. Sci., 2007, 49: 3659
25 Cheng X Q, Wang Y, Dong C F, et al. The beneficial galvanic effect of the constituent phases in 2205 duplex stainless steel on the passive films formed in a 3.5%NaCl solution [J]. Corros. Sci., 2018, 134: 122
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