Effect of Mo Addition on Corrosion Behavior of High-Entropy Alloys CoCrFeNiMox in Aqueous Environments

doi:10.1007/s40195-018-0812-7

Acta Metallurgica Sinica (English Letters) ›› 2019, Vol. 32 ›› Issue (1): 41-51.DOI: 10.1007/s40195-018-0812-7

所属专题： 2019年腐蚀专辑-2

收稿日期:2018-06-07 修回日期:2018-07-31 出版日期:2019-01-10 发布日期:2019-01-18
作者简介:
Dao-Kui Xu Professor of IMR, CAS, and “Young Merit Scholar” of Corrosion Center in the Institute of Metal Research (IMR), Chinese Academy of Sciences (CAS). He achieved Ph.D. degree from IMR, CAS, in 2008, during which he obtained “Chinese Academy of Sciences-BHP Billiton” Scholarship award, “Shi Changxu” Scholarship award and “Zhu-LiYueHua” Excellent Doctorate Student Scholarship of Chinese Academy of Sciences. He worked as a Research Fellow in ARC Center of Excellence, Design of Light Metals, Department of Materials Engineering, Monash University, Australia (2008.10-2011.10). He published more than 60 peer-reviewed scientific papers, attended 20 invited lectures and holds seven patents. His papers were cited more than 1200 times. His research interests mainly include: (1) fatigue behavior and fracture toughness of light metals, such as Mg, Al and Ti alloys; (2) effects of alloying, heat treatment and thermomechanical processes on the microstructural evolution and mechanical improvement of light metals; (3) corrosion, stress corrosion cracking and corrosion fatigue behavior of lightweight alloys; and (4) design of new lightweight alloys with a good balance of properties in terms of mechanical property and corrosion resistance.

Effect of Mo Addition on Corrosion Behavior of High-Entropy Alloys CoCrFeNiMo_x in Aqueous Environments

Xu-Liang Shang¹, Zhi-Jun Wang¹(), Qing-Feng Wu¹, Jin-Cheng Wang¹, Jun-Jie Li¹, Jia-Kang Yu¹

1. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China

Received:2018-06-07 Revised:2018-07-31 Online:2019-01-10 Published:2019-01-18
Contact: Wang Zhi-Jun
About author:
Author brief introduction:Dao-Kui Xu Professor of IMR, CAS, and “Young Merit Scholar” of Corrosion Center in the Institute of Metal Research (IMR), Chinese Academy of Sciences (CAS). He achieved Ph.D. degree from IMR, CAS, in 2008, during which he obtained “Chinese Academy of Sciences-BHP Billiton” Scholarship award, “Shi Changxu” Scholarship award and “Zhu-LiYueHua” Excellent Doctorate Student Scholarship of Chinese Academy of Sciences. He worked as a Research Fellow in ARC Center of Excellence, Design of Light Metals, Department of Materials Engineering, Monash University, Australia (2008.10-2011.10). He published more than 60 peer-reviewed scientific papers, attended 20 invited lectures and holds seven patents. His papers were cited more than 1200 times. His research interests mainly include: (1) fatigue behavior and fracture toughness of light metals, such as Mg, Al and Ti alloys; (2) effects of alloying, heat treatment and thermomechanical processes on the microstructural evolution and mechanical improvement of light metals; (3) corrosion, stress corrosion cracking and corrosion fatigue behavior of lightweight alloys; and (4) design of new lightweight alloys with a good balance of properties in terms of mechanical property and corrosion resistance.

摘要/Abstract

Abstract:

The corrosion behavior of CoCrFeNiMo_x alloys was investigated in aqueous environments, NaCl and H₂SO₄ solutions, respectively, to simulate typical neutral and acidic conditions. The cyclic polarization curves in NaCl and the potentiodynamic curves in H₂SO₄ clearly reveal the beneficial effects of Mo and the detrimental effect of σ-phase on the corrosion resistance. The X-ray photoelectron spectroscopy results of CoCrFeNiMo_x alloys in H₂SO₄ solution indicate that Cr and Mo predominate the corroded surface of the alloys, where Mo primarily exists in the form of MoO₃.

Key words: High-entropy alloys, Corrosion, σ-phase;, Molybdenum

. [J]. Acta Metallurgica Sinica (English Letters), 2019, 32(1): 41-51.

Xu-Liang Shang, Zhi-Jun Wang, Qing-Feng Wu, Jin-Cheng Wang, Jun-Jie Li, Jia-Kang Yu. Effect of Mo Addition on Corrosion Behavior of High-Entropy Alloys CoCrFeNiMo_x in Aqueous Environments[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(1): 41-51.

图/表 13

Fig. 1 Cyclic polarization curves of CoCrFeNiMox alloys in 3.5 wt% NaCl solution: ax?=?0.1; bx?=?0.2; cx?=?0.3; dx?=?0.4; ex?=?0.5

Table 1 Electrochemical parameters of CoCrFeNiMox alloys in 3.5 wt% NaCl solution

Designation	E_corr (mV vs. RE)	i_corr (μA/cm²)	E_pp (mV vs. RE)	i_pass (μA/cm²)	E_b (mV vs. RE)	E_prot (mV vs. RE)	E_rp (mV vs. RE)	ΔE (mV)
Mo_0.1	-?263	0.381	-?134	38	949	-	-?182	1083
Mo_0.2	-?131	0.072	-?28	16	941	747	184	969
Mo_0.3	-?257	0.766	-?181	50	955	11	-?178	1136
Mo_0.4	-?261	0.082	-?261	16	948	695	237	1209
Mo_0.5	-?261	0.738	-?100	24	965	370	63	1065

Fig. 2 SEM images of CoCrFeNiMox alloys in 3.5 wt% NaCl solution: ax?=?0.1; bx?=?0.2; cx?=?0.3; dx?=?0.4; ex?=?0.5; b’-e’ high magnification of Fig. 2b-e, respectively

Fig. 3 LSCM images of CoCrFeNiMox alloys after cyclic polarization in 3.5 wt% NaCl solution: a CoCrFeNiMo0.1, corrosion morphology; b CoCrFeNiMo0.1, topographic map; c CoCrFeNiMo0.3, corrosion morphology; d CoCrFeNiMo0.3, topographic map

Fig. 4 EDS maps of CoCrFeNiMo0.5 after cyclic polarization in 3.5 wt% NaCl for different elements

Fig. 5 a Bode, b Nyquist plots of CoCrFeNiMox alloys in the 3.5 wt% NaCl solution after different amounts of Mo addition; c, d corresponding equivalent electrical circuits (Z: impedance; Zre: real part of impedance; and Zim: imaginary part of impedance)

Fig. 6 aPotentiodynamic polarization curves of CoCrFeNiMox alloys in 0.5 mol/L H2SO4 solution, b magnification of curves around corrosion potential Ecorr

Table 2 Electrochemical parameters of CoCrFeNiMox alloys in 0.5 mol/L H2SO4 solution

Designation	E_corr (mV vs. RE)	i_corr (μA/cm²)	E_pp (mV vs. RE)	i_pass (μA/cm²)	E_b (mV vs. RE)	ΔE (mV)
Mo_0.1	-?688	9.666	-?638	30	469	1107
Mo_0.2	-?682	2.926	-?661	9	460	1121
Mo_0.3	-?694	8.626	-?656	30	453	1109
Mo_0.4	-?663	0.712	-?576	6	462	1038
Mo_0.5	-?632	1.526	-?536	12	450	986

Fig. 7 SEM images of CoCrFeNiMox alloys in 0.5 mol/L H2SO4 solution: ax?=?0.1; bx?=?0.2; cx?=?0.3; dx?=?0.4; ex?=?0.5; (c’-e’) high magnification of Fig. 7c-e, respectively

Fig. 8 LSCM images of CoCrFeNiMox alloys after potentiodynamic polarization in 0.5 mol/L H2SO4 solution: a CoCrFeNiMo0.1, corrosion morphology; b CoCrFeNiMo0.1, topographic map; c CoCrFeNiMo0.5, corrosion morphology; d CoCrFeNiMo0.5, topographic map

Table 3 Cationic fractions analyzed by XPS for CoCrFeNiMo0.4 potentiostatically polarized for 1 h in 0.5 mol/L H2SO4 solution

Potential (mV vs. RE)	Co	Cr	Fe	Ni	Mo
-?550	8.52	44.89	8.14	6.42	32.03
-?100	8.02	35.82	11.73	6.79	37.65
350	6.18	52.24	8.44	5.27	27.87

Fig. 9 Analytical results of XPS for CoCrFeNiMo0.4 potentiostatically polarized for 1 h in 0.5 mol/L H2SO4

Table 4 Summary of ratios for main elements with different oxidation states detected by XPS

Voltage (mV vs. RE)	Co²⁺/Co⁰	Cr³⁺/Cr⁰	Fe³⁺/Fe⁰	Ni²⁺/Ni⁰	Mo⁶⁺: Mo⁴⁺: Mo⁰
-?550	0.34	5.38	2.94	0	47.61: 16.59: 35.80
-?100	0.37	6.90	1.60	0.10	48.93: 17.11: 33.96
350	1.33	14.46	5.46	0.46	61.29: 15.54: 23.17

参考文献

[1]	B. Cantor, I. Chang, P. Knight, A. Vincent, Mater. Sci. Eng. A 375, 213 (2004)
[2]	J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau, S.Y. Chang, Adv. Eng. Mater. 6, 299(2004)
[3]	M.C. Gao, J.W. Yeh, P.K. Liaw, Y. Zhang, High-Entropy Alloys: Fundamentals and Applications (Springer, Berlin, 2016)
[4]	M.H. Tsai, J.W. Yeh, Mater. Res. Lett. 2, 107(2014)
[5]	W. Zhang, P.K. Liaw, Y. Zhang, Sci. China Mater. 61, 2(2018)
[6]	Y. Shi, B. Yang, P.K. Liaw, Metals 7, 43 (2017)
[7]	Y. Qiu, S. Thomas, M. Gibson, H.L. Fraser, N. Birbilis, N.P.J. Mater, Degradation 1, 15 (2017)
[8]	M.J. Yao, K.G. Pradeep, C.C. Tasan, D. Raabe, Scr. Mater. 72, 5(2014)
[9]	M.S. Lucas, G.B. Wilks, L. Mauger, J.A. Mu?oz, O.N. Senkov, E. Michel, J. Horwath, S.L. Semiatin, M.B. Stone, D.L. Abernathy, E. Karapetrova, Appl. Phys. Lett. 100, 251907(2012)
[10]	F. He, Z. Wang, Q. Wu, S. Niu, J. Li, J. Wang, C. Liu, Scr. Mater. 131, 42(2017)
[11]	Z. Wu, H. Bei, F. Otto, G.M. Pharr, E.P. George, Intermetallics 46, 131 (2014)
[12]	F. He, Z. Wang, Q. Wu, J. Li, J. Wang, C. Liu, Scr. Mater. 126, 15(2017)
[13]	X. Shang, Z. Wang, F. He, J. Wang, J. Li, J. Yu, Sci. China Technol.Soc. 61, 189(2018)
[14]	H. Yang, X. Shang, L. Wang, Z. Wang, J. Wang, X. Lin, Acta Metall.Sin. 54, 905(2018). (in Chinese)
[15]	X.W. Qiu, C.G. Liu, J. Alloys Compd. 553, 216(2013)
[16]	C. Shang, E. Axinte, J. Sun, X. Li, P. Li, J. Du, P. Qiao, Y. Wang, Mater. Des. 117, 193(2017)
[17]	Y.J. Hsu, W.C. Chiang, J.K. Wu, Mater. Chem. Phys. 92, 112(2005)
[18]	J.B. Cheng, X.B. Liang, B.S. Xu, Surf. Coat. Technol. 240, 184(2014)
[19]	Y. Shi, B. Yang, X. Xie, J. Brechtl, K.A. Dahmen, P.K. Liaw, Corros. Sci. 119, 33(2017)
[20]	C. Lee, Y. Chen, C. Hsu, J. Yeh, H. Shih, J. Electrochem. Soc. 154, C424(2007)
[21]	Y.X. Liu, C.Q. Cheng, J.L. Shang, W. Rui, L. Peng, Z. Jie, Trans. Nonferrous Met.Soc. 25, 1341(2015)
[22]	J. Cheng, D. Liu, X. Liang, B. Xu, Acta Metall. Sin.(Engl. Lett.) 27, 1031(2014)
[23]	Y.L. Chou, Y.C. Wang, J.W. Yeh, H.C. Shih, Corros. Sci. 52, 3481(2010)
[24]	Y. Chou, J. Yeh, H. Shih, Corros. Sci. 52, 2571(2010)
[25]	A. Pardo, M.C. Merino, A.E. Coy, F. Viejo, R. Arrabal, E. Matykina, Corros. Sci. 50, 1796(2008)
[26]	M. Ameer, A. Fekry, F.E. Heakal, Electrochim. Acta 50, 43 (2004)
[27]	J. Wanklyn, Corros. Sci. 21, 211(1981)
[28]	K. Hashimoto, K. Asami, K. Teramoto, Corros. Sci. 19, 3(1979)
[29]	K. Sugimoto, Y. Sawada, Corros. Sci. 17, 425(1977)
[30]	K. Sugimoto, Y. Sawada, Corrosion 32, 347 (1976)
[31]	A. Mishra, S. Ramamurthy, M. Biesinger, D. Shoesmith, Electrochim. Acta 100, 118 (2013)
[32]	J. Hayes, J. Gray, A. Szmodis, C. Orme, Corrosion 62, 491 (2006)
[33]	A. Tomio, M. Sagara, T. Doi, H. Amaya, N. Otsuka, T. Kudo, Corros. Sci. 98, 391 (2015)
[34]	Y. Lu, C. Clayton, J. Electrochem. Soc. 132, 2517(1985)
[35]	A. Brooks, C. Clayton, K. Doss, Y. Lu, J. Electrochem. Soc. 133, 2459(1986)
[36]	C. Clayton, Y. Lu, J. Electrochem. Soc. 133, 2465(1986)
[37]	C. Clayton, Y. Lu, Corros. Sci. 29, 881(1989)
[38]	Y. Lu, C. Clayton, A. Brooks, Corros. Sci. 29, 863(1989)
[39]	M. Pourbaix, J.A. Franklin, Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd edn. (NACE International, Houston, 1974)
[40]	W. Yang, R.C. Ni, H.Z. Hua, A. Pourbaix, Corros. Sci. 24, 691(1984)
[41]	K. Hashimoto, K. Asami, A. Kawashima, H. Habazaki, E. Akiyama, Corros. Sci. 49, 42(2007)
[42]	H. Habazaki, A. Kawashima, K. Asami, K. Hashimoto, Corros. Sci. 33, 225(1992)
[43]	Z. Szklarska-Smialowska, Pitting Corrosion of Metals (NACE, Houston, 1986)
[44]	M.W. Tan, E. Akiyama, A. Kawashima, K. Asami, K. Hashimoto, Corros. Sci. 37, 1289(1995)
[45]	C. Leygraf, G. Hultquist, I. Olefjord, B.O. Elfstr?m, V. Knyazheva, A. Plaskeyev, Y.M. Kolotyrkin, Corros. Sci. 19, 343(1979)
[46]	A. Irhzo, Y. Segui, N. Bui, F. Dabosi, Corrosion 42, 141 (1986)
[47]	T. Wijesinghe, D.J. Blackwood, Corros. Sci. 50, 23(2008)
[48]	T.T. Shun, L.Y. Chang, M.H. Shiu, Mater. Charact. 70, 63(2012)
[49]	W. Liu, Z. Lu, J. He, J. Luan, Z. Wang, B. Liu, Y. Liu, M. Chen, C. Liu, Acta Mater. 116, 332(2016)
[50]	B. Wilde, Corrosion 28, 283 (1972)
[51]	K. Ogura, T. Ohama, Corrosion 40, 47 (1984)
[52]	G. Frankel, J. Electrochem. Soc.145, 2186 (1998)
[53]	W. Tian, N. Du, S. Li, S. Chen, Q. Wu, Corros. Sci. 85, 372(2014)
[54]	X. Shang, Z. Wang, F. He, J. Wang, J. Li, J. Yu, Sci. China Technol.Sci. 61, 2(2017)
[55]	P. Bommersbach, C. Alemany-Dumont, J.P. Millet, B. Normand, Electrochim. Acta 51, 1076 (2005)
[56]	L. Liu, Y. Li, F. Wang, Electrochim. Acta 52, 7193 (2007)
[57]	A.S. Hamdy, E. Shenawy, T. Bitar, Int. J. Electrochem.Soc. 1, 171(2006)
[58]	A. Pardo, M.C. Merino, A.E. Coy, F. Viejo, R. Arrabal, E. Matykina, Corros. Sci. 50, 780(2008)
[59]	N. McIntyre, M. Cook, Anal. Chem. 47, 2208(1975)
[60]	T. Chuang, C. Brundle, D. Rice, Surf. Sci. 59, 413(1976)
[61]	G.C. Allen, P.M. Tucker, P.K. Wild, J. Chem. Soc. 74, 1126(1978)
[62]	J. Leiro, E. Minni, Philos. Mag. B 49, L61 (1984)
[63]	C.E. Myers, H.F. Franzen, J.W. Anderegg, Inorg. Chem. 24, 1822(1985)
[64]	V. Nefedov, Y.V. Salyn, G. Leonhardt, R. Scheibe, J. Electron Spectrosc.Relat. Phenom. 10, 121(1977)
[65]	C. Wagner, W. Rigg, L. Davis, J. Moulder, G. Muilenberg, Handbook of X-ray Photoelectron Spectroscopy (Perkin-Elmer Corporation, Eden Prairie, 1979)
[66]	C.P. Li, A. Proctor, D.M. Hercules, Appl. Spectrosc. 38, 880(1984)
[67]	M.C. Biesinger, B.P. Payne, A.P. Grosvenor, L.W. Lau, A.R. Gerson, R. Smart, Appl. Surf. Sci. 257, 2717(2011)
[68]	D. Zingg, L.E. Makovsky, R. Tischer, F.R. Brown, D.M. Hercules, J. Phys. Chem. 84, 2898(1980)
[69]	H. Yao, R. Baird, H. Gandhi, J. Catal. 84, 8(1983)
[70]	J. Simmons, Mater. Sci. Eng. A 207, 159 (1996)
[71]	J.O. Nilsson, Mater. Sci. Technol. 8, 685(1992)
[72]	D.Y. Kobayashi, S. Wolynec, Mater. Res. 2, 239(1999)
[73]	X.H. Zhao, Z.Q. Bai, Y.R. Feng, A.Q. Fu, Appl. Mech. Mater. 184, 1038(2002)
[74]	J. Michalska, M. Sozańska, Mater. Charact. 56, 355(2006)
[75]	H.M. Ezuber, A. Houd, F. Shawesh, Desalination 207, 268 (2007)
[76]	J. Xu, C. Zhuo, J. Tao, S. Jiang, Appl. Surf. Sci. 255, 2688(2008)
[77]	K. Adhe, V. Kain, K. Madangopal, H. Gadiyar, J. Mater. Eng.Perform. 5, 500(1996)

Effect of Mo Addition on Corrosion Behavior of High-Entropy Alloys CoCrFeNiMo_x in Aqueous Environments

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献

相关文章 0

编辑推荐

Metrics

本文评价