<strong>Mo</strong>含量对<strong>CoCrFeNiMo</strong>高熵合金组织及耐蚀性能的影响

doi:10.11901/1005.3093.2020.269

材料研究学报

2020, Vol. 34

Issue (11): 868-874 DOI: 10.11901/1005.3093.2020.269

研究论文

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Mo含量对CoCrFeNiMo高熵合金组织及耐蚀性能的影响

刘谦¹(

), 王昕阳¹, 黄燕滨¹, 谢璐², 许诠³, 李林虎¹

^1.陆军装甲兵学院装备保障与再制造系北京 100072
^2.北京科技大学机械工程学院北京 100083
^3.中国卫星海上测控部江阴 214431

Effect of Molybdenum Content on Microstructure and Corrosion Resistance of CoCrFeNiMo High Entropy Alloy

LIU Qian¹(

), WANG Xinyang¹, HUANG Yanbin¹, XIE Lu², XU Quan³, LI Linhu¹

^1.Army Academy of Armored Forces, Equipment Support and Remanufacturing Department, Beijing 100072, China
^2.University of Science & Technology Beijing, Institute of Mechanical Engineering, Beijing 100083, China
^3.China Satellite Maritime Measurement and Control Department, Jiangyin 214431, China

引用本文:

刘谦, 王昕阳, 黄燕滨, 谢璐, 许诠, 李林虎. Mo含量对CoCrFeNiMo高熵合金组织及耐蚀性能的影响[J]. 材料研究学报, 2020, 34(11): 868-874.
Qian LIU, Xinyang WANG, Yanbin HUANG, Lu XIE, Quan XU, Linhu LI. Effect of Molybdenum Content on Microstructure and Corrosion Resistance of CoCrFeNiMo High Entropy Alloy[J]. Chinese Journal of Materials Research, 2020, 34(11): 868-874.

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摘要:

高熵合金由于具有优异的机械性能及耐蚀性能在涂层工业领域备受关注。采用同步送粉激光熔覆技术在Q235钢表面制备了CoCrFeNiMo_x高熵合金涂层，研究了涂层的组织结构和耐蚀性能，并结合第一性原理计算分析了涂层耐蚀机理。研究结果表明：CoCrFeNiMo_0.1、CoCrFeNiMo_0.2高熵合金涂层是由fcc相组成，而CoCrFeNiMo_0.3高熵合金涂层则由fcc相和σ相组成。合金的晶粒主要呈树枝晶，枝晶间富集Cr、Mo元素，枝晶内富集Co、Fe元素。在3.5%(质量分数)NaCl溶液中，CoCrFeNiMo_x高熵合金涂层具有优良的综合耐蚀性能；并且随着Mo元素含量的增加，涂层的腐蚀电位正移，腐蚀电流密度减少，钝化区间变长，阻抗弧半径增大，电极反应阻力增强。通过第一性原理计算证明，涂层较高的耐蚀性能与表面致密的钝化膜形成密切相关。

关键词 ：金属材料, 耐蚀性能, 第一性原理, 高熵合金, 激光熔覆涂层

Abstract：

High entropy alloys have been extensively paid attention in the coating industry due to their excellent mechanical properties and corrosion resistance. CoCrFeNiMo_x high-entropy alloy coatings were prepared on the surface of Q235 steel by laser cladding with synchronous powder feeding. The microstructure, microhardness and corrosion resistance of the coatings were studied. The corrosion mechanism of the alloys was analyzed and the strengthening mechanism of their corrosion resistance was revealed combined with the first-principle calculation. The results show that CoCrFeNiMo_0.1 and CoCrFeNiMo_0.2 are composed of the fcc phase. The fcc phase and tetragonal CrMo phase are both observed in the CoCrFeNiMo_0.3 high-entropy alloy layer. The microstructure of the alloys is composed of dendrites. Cr and Mo elements are enriched in the interdendritic, and Co and Fe elements are enriched in the dendrites. CoCrFeNiMo_x high-entropy alloys have excellent comprehensive corrosion resistance in 3.5% (mass fraction) NaCl solution. As the content of Mo increases, the corrosion potential shifts to more positive potentials, the corrosion current density decreases, the length of polarization region increases, the impedance arc radius increases, and the electrode reaction resistance increases. It is found via the first-principle calculation that the higher corrosion resistance of the coating is related to its dense passivation film.

Key words： metallic materials corrosion resistance first principle high entropy alloy laser cladding coating

收稿日期: 2020-07-02

ZTFLH:

TG131

作者简介: 王昕阳，男，1995年生，硕士

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https://www.cjmr.org/CN/10.11901/1005.3093.2020.269 或 https://www.cjmr.org/CN/Y2020/V34/I11/868

图1 CoCrFeNiMox高熵合金涂层的XRD图

图2 CoCrFeNiMox激光熔覆涂层截面的组织形貌

表1 CoCrFeNiMox激光熔覆涂层各区域的组元元素分布(原子分数，%)

图3 CoCrFeNiMox高熵合金涂层在3.5%的NaCl溶液中的极化曲线

表2 各组高熵合金的电化学参数

图4 Mo1组和Mo3组涂层在3.5%NaCl中的阻抗谱

图5 涂层阻抗谱的等效电路图

表3 涂层的EIS拟合参数

表4 高熵合金钝化膜的Cl-吸附能和扩散能

1	Gaskell. Introduction to the Thermodynmics of Materials [M]. USA, Boca Raton: CRC Press, 2008
2	Cao L G, Zhu L, Zhang L L, et al. Microstructure evolution and mechanical properties of rapid solidified AlCoCrFeNi_2.1 eutectic high entropy alloy [J]. Chin. J. Mater. Res., 2019, 33: 650
2	曹雷刚, 朱琳, 张磊磊等. 快速凝固AlCoCrFeNi_2.1共晶高熵合金的微观组织演变和力学性能 [J]. 材料研究学报, 2019, 33: 650
3	Yeh J W, Chen S K, Lin S J, et al. Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes [J]. Adv. Eng. Mater., 2004, 6: 299
4	Miracle D B, Senkov O N. A critical review of high entropy alloys and related concepts [J]. Acta Mater., 2017, 122: 448
5	Liu N, Chen C, Chang I, et al. Compositional dependence of phase selection in coCrCu_0.1FeMoNi-based high-entropy alloys [J]. Materials, 2018, 11: 1290
6	Gao N, Long Y, Peng H Y, et al. Microstructure and mechanical properties of TiVNbTa refractory high-entropy alloy prepared by powder metallurgy [J]. Chin. J. Mater. Res., 2019, 33: 572
6	高楠, 龙雁, 彭海燕等. 粉末冶金TiVNbTa难熔高熵合金的组织和力学性能 [J]. 材料研究学报, 2019, 33: 572
7	Liu W H, He J Y, Huang H L, et al. Effects of Nb additions on the microstructure and mechanical property of CoCrFeNi high-entropy alloys [J]. Intermetallics, 2015, 60: 1
8	Wang Z H, Wang H, He D Y, et al. Microstructure characterization of CoCrCuFeNiMn high entropy alloys by plasma cladding [J]. Rare Met. Mater. Eng., 2015, 44: 644
8	王智慧, 王虎, 贺定勇等. 等离子熔覆CoCrCuFeNiMn高熵合金组织研究 [J]. 稀有金属材料与工程, 2015, 44: 644
9	Liu N, Zhu Z X, Jin Y X, et al. Research progress of laser cladding technology to prepare high-entropy alloy coatings [J]. Mater. Rev., 2014, 28(5): 133
9	刘宁, 朱智轩, 金云学等. 激光熔覆技术制备高熵合金涂层的研究进展 [J]. 材料导报, 2014, 28(5): 133
10	He F, Wang Z J, Wang J, et al. Abnormal γ″-ε phase transformation in the CoCrFeNiNb_0.25 high entropy alloy [J]. Scripta Mater., 2018, 146: 281
11	Wang W R, Qi W, Xie L, et al. Microstructure and corrosion behavior of (CoCrFeNi)₉₅Nb₅ high-entropy alloy coating fabricated by plasma spraying [J]. Materials, 2019, 12: 694
12	Liu L, Qi J G, Wang B, et al. Microstructure and mechanical properties of CoCrFeNiV_x high entropy alloys [J]. Spec. Cast. Nonferrous Alloys, 2015, 35: 1130
12	刘亮, 齐锦刚, 王冰等. CoCrFeNiV_x高熵合金的组织与力学性能 [J]. 特种铸造及有色合金, 2015, 35: 1130
13	Wang W R, Wang J Q, Yi H G, et al. Effect of molybdenum additives on corrosion behavior of (CoCrFeNi)_100-_xMo_x high-entropy alloys [J]. Entropy, 2018, 20: 908
14	Liu Q, Wang X Y, Huang Y B, et al. Research progress on high-entropy alloy design and computer simulation [J]. Mater. Rev., 2019, 33(): 392
14	刘谦, 王昕阳, 黄燕滨等. 高熵合金设计与计算机模拟方法的研究进展 [J]. 材料导报, 2019, 33(): 392
15	Shi D M, Wen B, Melnik R, et al. First-principles studies of Al-Ni intermetallic compounds [J]. J. Solid State Chem., 2009, 182: 2664
16	Wang L X. The first-principle studies on mechanical properties of AlFeCrCuX high entropy alloys [D]. Dalian: Dalian University of Technology, 2017
16	王兰馨. AlFeCrCuX高熵合金力学性能的第一性原理计算 [D]. 大连: 大连理工大学, 2017
17	Huang S, Li X Q, Huang H, et al. Mechanical performance of FeCrCoMnAl_x high-entropy alloys from first-principle [J]. Mater. Chem. Phys., 2018, 210: 37
18	Nong Z S, Zhu J C, Yu H L, et al. First principles calculation of intermetallic compounds in FeTiCoNiVCrMnCuAl system high entropy alloy [J]. Trans. Nonferrous Met. Soc. China, 2012, 22: 1437
19	Shun T T, Chang L Y, Shiu M H. Microstructures and mechanical properties of multiprincipal component CoCrFeNiTi_x alloys [J]. Mater. Sci. Eng., 2012, 556A: 170
20	Wong S K, Shun T T, Chang C H, et al. Microstructures and properties of Al_0.3CoCrFeNiMn_x high-entropy alloys [J]. Mater. Chem. Phys., 2017, 210: 146
21	Wang Y F, Ma S G, Chen X H, et al. Optimizing mechanical properties of AlCoCrFeNiTi_x high-entropy alloys by tailoring microstructures [J]. Acta Metall. Sin. Eng. Lett., 2013, 26: 277
22	Chen Q S, Dong Y, Zhang J J, et al. Microstructure and properties of AlCoCrFeNiB_x(x=0, 0.1, 0.25, 0.5, 0.75, 1.0) high entropy alloys [J]. Rare Met. Mater. Eng., 2017, 46: 651
22	陈秋实, 董勇, 张峻嘉等. AlCoCrFeNiB_x(x=0, 0.1, 0.25, 0.5, 0.75, 1.0)高熵合金的微观结构与性能 [J]. 稀有金属材料与工程, 2017, 46: 651
23	Wang X Y, Liu Q, Huang Y B, et al. Effect of Ti content on the microstructure and corrosion resistance of CoCrFeNiTi_x high entropy alloys prepared by laser cladding [J]. Materials, 2020, 13(10): 2209
24	Xu Q, Huang Y B, Liu Q, et al. Characterization and corrosion resistance study of laser-clad (CoCrFeNi)₉₅Nb₅ high-entropy alloy coating [J]. Electroplat. Finish., 2019, 38: 536
24	许诠, 黄燕滨, 刘谦等. 激光熔覆法制备(CoCrFeNi)₉₅Nb₅高熵合金涂层的表征与耐蚀性研究 [J]. 电镀与涂饰, 2019, 38: 536
25	Zhang B. XPS and first-principles study on electrochemical corrosion behavior of sputtered Fe-Cr alloys nanocrystalline thin films [D]. Dalian: Dalian University of Technology, 2016
25	张滨. Fe-Cr合金溅射纳米晶薄膜腐蚀电化学行为的XPS及第一性原理计算的研究 [D]. 大连: 大连理工大学, 2016
26	An X L. The microstructure and properties of high entropy alloy Ti_xFeCoCrWSi coating synthesised by laser cladding [D]. Guiyang: Guizhou University, 2015
26	安旭龙. 激光熔覆制备Ti_xFeCoCrWSi高熵合金组织与性能研究 [D]. 贵阳: 贵州大学, 2015
27	Li Q H, Yue T M, Guo Z N, et al. Microstructure and corrosion properties of AlCoCrFeNi high entropy alloy coatings deposited on AISI 1045 steel by the electrospark process [J]. Metall. Mater. Trans., 2013, 44A: 1767
28	Lee C P, Chen Y Y, Hsu C Y, et al. The effect of boron on the corrosion resistance of the high entropy alloys Al_0.5CoCrCuFeNiB_x [J]. J. Electrochem. Soc., 2007, 154: C424
29	Shang C Y, Axinte E, Sun J, et al. CoCrFeNi (W_1-_xMo_x) high-entropy alloy coatings with excellent mechanical properties and corrosion resistance prepared by mechanical alloying and hot pressing sintering [J]. Mater. Des., 2017, 117: 193
30	Qiu X W, Liu C G. Microstructure and properties of Al₂CrFeCoCuTiNi_x high-entropy alloys prepared by laser cladding [J]. J. Alloys Compd., 2013, 553: 216
31	Jiang H, Jiang L, Li D X, et al. Effect of Niobium on microstructure and properties of the CoCrFeNb_xNi high entropy alloys [J]. J. Mater. Sci. Technol., 2017, 33: 712

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