Improving high-temperature oxidation behavior by modifying Al and Co content in Al-Co-Cr-Fe-Ni high-entropy alloy

doi:10.1016/j.jmst.2022.04.028

Abstract

Abstract:

Composition modification was introduced to improve the oxidation resistance by varying Al and excluding Co from the Al-Co-Cr-Fe-Ni system. Since adjusting the composition shifted the valence electron concentration (VEC) of the alloys, the dual-phase structure of the alloys is expected to be more stable. At low temperatures (T < 1273 K), the alloys formed mixed oxide products. As oxidation temperature increased, only Cr₂O₃ or Al₂O₃ dominated the alloy's surface. Compared to equiatomic AlCoCrFeNi (5-Equi), non-equiatomic AlCoCrFeNi (5-B 40) and four-component AlCrFeNi (4-B 2013) had better oxidation resistance due to monocrystalline-Al₂O₃ formation. Besides the role of oxide formation, maintaining BCC and B2 phases within the alloys is also beneficial to supporting the stable Cr₂O₃ or Al₂O₃.

Key words: High-entropy alloy, Alloy design, Oxidation, Valence electron concentration, Phase stability, Transmission electron microscope

Timothy Alexander Listyawan, Maya Putri Agustianingrum, Young Sang Na, Ka Ram Lim, Nokeun Park. Improving high-temperature oxidation behavior by modifying Al and Co content in Al-Co-Cr-Fe-Ni high-entropy alloy[J]. J. Mater. Sci. Technol., 2022, 129: 115-126.

Figures/Tables 17

Table 1. Chemical composition (at.%) of the alloys characterized by APT [11].

Alloys		Al	Co	Cr	Fe	Ni
5-Equi	Nominal	20	20	20	20	20
	BCC	1.4	21.5	42.0	30.5	4.6
	B2	30.3	20.2	5.2	13.9	30.4
5-B 40	Nominal	12.9	20.9	27.3	24	14.9
	BCC	1.5	21.5	40.2	32.2	4.7
	B2	28.6	22.3	2.6	17.0	29.5
4-B 2013	Nominal	13.6	-	13.3	61.9	11.2
	BCC	7.3	-	17.2	73.3	2.1
	B2	38.7	-	1.3	17.8	42.1

Fig. 1. Square of mass-gain per surface area versus oxidation time curves of the alloys for 48 h at: (a) 1173, (b) 1243, (c) 1323, and (d) 1373 K.

Fig. 2. XRD patterns on the surface of the alloys after oxidation for 48 h at: (a) 1173, (b) 1243, (c) 1323, and (d) 1373 K.

Fig. 3. Microstructure of 5-Equi after oxidation at 1323 K for 48 h. (a) Representative SEM-BSE image, giving an overview of oxide layer and base metal. High magnification BF-TEM images including elemental mappings and SADPs of (b-d) oxide layer and (e-g) base metal. Red circles in (b) and (e) indicate where the SADPs were obtained from the oxide layer and base metal, respectively.

Fig. 4. Microstructure of 5-B 40 after oxidation at 1323 K for 48 h. (a) High magnification BF-TEM images including (b) elemental mappings and (c) SADPs. Red circles in (a) indicate where the SADPs were obtained from the oxide layer and base metal, respectively.

Fig. 5. Microstructure of 4-B 2013 after oxidation at 1323 K for 48 h. (a) High magnification BF-TEM images including (b) elemental mappings and (c) SADPs. Red circles in (a) indicate where the SADPs were obtained from the oxide layer and base metal, respectively.

Table 2. TEM-EDS result of 5-Equi after oxidation at 1323 K for 48 h.

Points	Composition (at.%)						Phase
Points	Al	Co	Cr	Fe	Ni	O	Phase
1	0.10	0.21	39.88	0.32	0.15	59.34	Cr₂O₃
2	0.35	25.05	23.89	31.58	14.27	4.85	FCC
3	3.58	23.60	22.89	30.01	13.52	6.40	B2
4	38.71	4.40	4.51	5.87	2.52	43.99	Al₂O₃
5	0.37	25.47	25.51	31.63	14.92	2.09	FCC

Table 3. TEM-EDS result of 5-B 40 after oxidation at 1323 K for 48 h.

Points	Composition (at.%)						Phase
Points	Al	Co	Cr	Fe	Ni	O	Phase
1	59.75	0.20	0.28	0.07	0.19	39.51	Al₂O₃
2	2.40	23.97	29.87	28.37	12.68	2.72	FCC
3	18.15	22.96	6.61	14.16	37.60	0.52	B2
4	2.64	24.47	29.05	31.30	12.54	0.00	BCC

Table 4. TEM-EDS result of 4-B 2013 after oxidation at 1323 K for 48 h.

Points	Composition (at.%)					Phase
Points	Al	Cr	Fe	Ni	O	Phase
1	37.75	0.96	0.45	0.16	60.68	Al₂O₃
2	3.06	17.56	75.56	2.77	1.05	BCC
3	15.66	3.35	26.39	54.60	0.00	B2

Fig. 6. Arrhenius plot of kp values from 5-Equi, 5-B 40, and 4-B 2013 after oxidation test.

Table 5. Activation energies (Ea) 5-Equi, 5-B 40, and 4-B 2013 after oxidation test.

Alloys	E_a (kJ mol⁻¹)
Alloys	Range I (1323-1373 K)	Range II (1173-1323 K)
5-Equi	324.3	10.5
5-B 40	330.9	16.8
4-B 2013	473.9	29.3

Fig. 7. Schematic description of high-temperature oxidation of 5-Equi at different oxidation temperatures.

Fig. 8. Schematic description of high-temperature oxidation of 5-B 40 at different oxidation temperatures.

Fig. 9. Schematic description of high-temperature oxidation of 4-B 2013 at different oxidation temperatures.

Fig. 10. (a) Relationship between calculated VEC and oxidation rate and (b) the plot of oxidation rate vs. FCC phase fraction after oxidation at 1323 K.

Fig. 11. The oxidation rate comparison of the present experiment work with the other materials at various temperatures.

Table 6. Oxidation activation energies determined from present study and commercial alloys in different oxidation duration and temperature ranges.

Alloys	Activation energy (kJ mol⁻¹)	Temperature range (K)	Oxidation duration (h)	Refs.
5-Equi	324.3	1323-1373	±48	This work
5-B 40	330.9	1323-1373	±48	This work
4-B 2013	473.9	1323-1373	±48	This work
Al_0.5CoCrFeNi	143.5	1073-1273	±72	[58]
Al_0.6CrFeNi	291.8	1073-1273	±100	[59]
Al_0.6CrFeNiSi_0.3	270.2	1073-1273	±100	[59]
SS 439 (Ferritic Stainless Steel)	251.9	1123-1073	±55	[60]
P92 (Martensitic Stainless Steel)	466.1	973-1223	±24	[61]
Fe(SiCrNi) alloy	243	1123-1323	±7-277	[62]
Fe (MnSiCrNiCe) alloy	133.8	1123-1323	±7-277	[62]
Astroloy Ni-based alloy	270	1173-1273	±70	[63]
Waspaloy Ni-based alloy	300	1173-1273	±100	[63]
Udimet 720 Ni-based alloy	250	1173-1273	±100	[63]

References 63

[1]	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 (2004) 299-303. DOI URL
[2]	J.Y. He, H. Wang, H.L. Huang, X.D. Xu, M.W. Chen, Y. Wu, X.J. Liu, T.G. Nieh, K. An, Z.P. Lu, Acta Mater. 102 (2016) 187-196. DOI URL
[3]	C.Y. Hsu, T.S. Sheu, J.W. Yeh, S.K. Chen, Wear 268 (2010) 653-659. DOI URL
[4]	S. Guo, C.T. Liu, Prog. Nat. Sci. Mater. Int. 21 (2011) 433-446. DOI URL
[5]	X.F. Wang, Y. Zhang, Y. Qiao, G.L. Chen, Intermetallics 15 (2007) 357-362. DOI URL
[6]	N.D. Stepanov, D.G. Shaysultanov, G.A. Salishchev, M.A. Tikhonovsky, E.E. Oleynik, A.S. Tortika, O.N. Senkov, J. Alloy. Compd. 628 (2015) 170-185. DOI URL
[7]	Y.P. Wang, B.S. Li, M.X. Ren, C. Yang, H.Z. Fu, Mater. Sci. Eng. A 491 (2008) 154-158. DOI URL
[8]	K.R. Lim, K.S. Lee, J.S. Lee, J.Y. Kim, H.J. Chang, Y.S. Na, J. Alloy. Compd. 728 (2017) 1235-1238. DOI URL
[9]	A. Munitz, S. Salhov, G. Guttmann, N. Derimow, M. Nahmany, Mater. Sci. Eng. A 742 (2019) 1-14. DOI URL
[10]	C. Zhang, F. Zhang, H. Diao, M.C. Gao, Z. Tang, J.D. Poplawsky, P.K. Liaw, Mater. Des. 109 (2016) 425-433. DOI URL
[11]	K.R. Lim, H.J. Kwon, J.H. Kang, J.W. Won, Y.S. Na, Mater. Sci. Eng. A 771 (2020) 138638. DOI URL
[12]	W.R. Wang, W.L. Wang, J.W. Yeh, J. Alloy. Compd. 589 (2014) 143-152. DOI URL
[13]	M.P. Agustianingrum, F.H. Latief, N. Park, U. Lee, Intermetallics 120 (2020) 106757. DOI URL
[14]	T.M. Butler, M.L. Weaver, J. Alloy. Compd. 674 (2016) 229-244. DOI URL
[15]	A. Anupam, A. S.M. Ang, K. Guruvidyathri, M. Abbas, D. Sivaprahasam, P. Munroe, C.C. Berndt, B.S. Murty, R.S. Kottada, Corros. Sci. 184 (2021) 109381. DOI URL
[16]	M.P. Agustianingrum, U. Lee, N. Park, Corros. Sci. 173 (2020) 108755. DOI URL
[17]	S.F. Frederick, I. Cornet, J. Electrochem. Soc. 102 (1955) 279-284. DOI URL
[18]	Z. Jiang, W. Chen, Z. Xia, W. Xiong, Z. Fu, Intermetallics 108 (2019) 45-54. DOI URL
[19]	F. Kaya, M. Yeti ¸s, G.İ. Selimoğlu, B. Derin, Eng. Sci. Technol. Int. J. (2021).
[20]	Y. Dong, Z. Yao, X. Huang, F. Du, C. Li, A. Chen, F. Wu, Y. Cheng, Z. Zhang, J. Alloy. Compd. 823 (2020) 153886. DOI URL
[21]	K.C. Lo, Y.J. Chang, H. Murakami, J.W. Yeh, A.C. Yeh, Sci. Rep. 9 (2019) 1-12. DOI URL
[22]	X. Cheng, Z. Jiang, D. Wei, J. Zhao, B.J. Monaghan, R.J. Longbottom, L. Jiang, Met. Mater. Int. 21 (2015) 251-259. DOI URL
[23]	A. Atkinson, Mater. Sci. Technol. 4 (1988) 1046-1051 (United Kingdom). DOI URL
[24]	G. Laplanche, U.F. Volkert, G. Eggeler, E.P. George, Oxid. Met. 85 (2016) 629-645. DOI URL
[25]	K.Y. Tsai, M.H. Tsai, J.W. Yeh, Acta Mater. 61 (2013) 4 887-4 897.
[26]	Q. Li, W. Chen, J. Zhong, L. Zhang, Q. Chen, Z.K. Liu, Materials 8 (2018)(Basel).
[27]	P. Kofstad, High Temperature Oxidation of Metals, John Wiley and Sons, Inc., New York, 1966.
[28]	A.S. Dorcheh, M. Schütze, M.C. Galetz, Corros. Sci. 130 (2018) 261-269. DOI URL
[29]	P. Šulhánek, M. Drienovský, I. ˇCerniˇ cková, L. Duriška, R. Skaudžius, Ž. Gerhá- tová, M. Palcut, Materials 13 (2020) 3152 (Basel).
[30]	S. Cruchley, H.E. Evans, M.P. Taylor, M.C. Hardy, S. Stekovic, Corros. Sci. 75 (2013) 58-66. DOI URL
[31]	M. Gemmaz, M. Afyouni, A. Mosser, Surf. Sci. 227 (1990) L109-L111.
[32]	H. Mehrer, M. Luckabauer, W. Sprengel, Defect Diffus. Forum 333 (2013) 1-25.
[33]	Y. Li, P. Zhang, J. Zhang, Z. Chen, B. Shen, Corros. Sci. 190 (2021) 109633. DOI URL
[34]	J.A. Dean, Lange’s Handbook of Chemistry, 15th ed, McGraw-Hill Professional, New York, 1999.
[35]	A.S. Khanna, Handb. Environ. Degrad. Mater. 2 (2018) 117-132.
[36]	Y. Inoue, N. Hiraide, A. Hayashi, K. Ushioda, ISIJ Int. 58 (2018) 1850-1859. DOI URL
[37]	C. Zhao, Y. Zhou, Z. Zou, L. Luo, X. Zhao, F. Guo, P. Xiao, Corros. Sci. 126 (2017) 334-343. DOI URL
[38]	D. Ko, Y. Shin, J. Weld. Join. 36 (2018) 8-13.
[39]	D. Ko, Y.I. Park, Y. Shin, J. Weld. Join. 38 (2020) 528-534. DOI URL
[40]	D. Caplan, G.I. Sproule, Oxid. Met. 9 (1975) 459-472. DOI URL
[41]	J. Lu, Y. Chen, H. Zhang, N. Ni, L. Li, L. He, R. Mu, X. Zhao, F. Guo, Corros. Sci. 166 (2020) 108426. DOI URL
[42]	T.J. Nijdam, L.P.H. Jeurgens, J.H. Chen, W.G. Sloof, Oxid. Met. 64 (2005) 355-377. DOI URL
[43]	F. Gesmundo, B. Gleeson, Oxid. Met. 44 (1995) 211-237. DOI URL
[44]	R. Prescott, M.J. Graham, Oxid. Met. 38 (1992) 233-254. DOI URL
[45]	V.K. Tolpygo, D.R. Clarke, Mater. High Temp. 17 (20 0 0) 59-70. DOI URL
[46]	R.R. Adharapurapu, J. Zhu, V.S. Dheeradhada, D.M. Lipkin, T.M. Pollock, Acta Mater. 76 (2014) 449-462. DOI URL
[47]	W. Brandl, H.J. Grabke, D. Toma, J. Krüger, Surf. Coat. Technol. 86-87 (1996) 41-47.
[48]	B. Pint, Solid State ionics 78 (1995) 99-107. DOI URL
[49]	D.B. Miracle, Acta Metall. Mater. 41 (1993) 64 9-6 84.
[50]	H. Li, S. Tao, Z. Zhou, L. Sun, A. Hesnawi, S. Gong, Surf. Coat. Technol. 201 (2007) 6589-6592. DOI URL
[51]	M.P. Brady, I.G. Wright, B. Gleeson, JOM 52 (20 0 0) 16-21.
[52]	J. Lu, J. Huang, Z. Yang, Y. Zhou, Y. Dang, X. Zhao, Y. Yuan, Oxid. Met. 89 (2018) 197-209. DOI URL
[53]	I. Barin, Thermochemical Data of Pure Substances, 3rd ed, VCH Verlagsge- sellschaft mbH, Weinheim, 1995.
[54]	N.P. Padture, M. Gell, E.H. Jordan, Science 296 (2002) 280-284. PMID
[55]	H. Bei, G.M. Pharr, E.P. George, J. Mater. Sci. 39 (2004) 3975-3984. DOI URL
[56]	R. Chen, G. Qin, H. Zheng, L. Wang, Y. Su, Y.L. Chiu, H. Ding, J. Guo, H. Fu, Acta Mater. 144 (2018) 129-137. DOI URL
[57]	S. Guo, C. Ng, J. Lu, C.T. Liu, J. Appl. Phys. 109 (2011) 103505. DOI URL
[58]	S. Abbaszadeh, A. Pakseresht, H. Omidvar, A. Shaﬁei, Surf. Interf. 21 (2020) 100724.
[59]	L. Chen, Z. Zhou, Z. Tan, D. He, K. Bobzin, L. Zhao, M. Öte, T. Königstein, J. Alloy. Compd. 764 (2018) 845-852. DOI URL
[60]	A .C.S. Sabioni, A .M. Huntz E.C. Da Luz, M. Mantel C. Haut, Mater. Res. 6 (2003) 179-185. DOI URL
[61]	J. Yuan, X. Wu, W. Wang, S. Zhu, F. Wang, Materials 7 (2014) 2772-2783 (Basel). DOI URL
[62]	V.F. De Souza, A.J. Araújo, J.L. Do Nascimento Santos, C.A. Della Rovere, A.M. De Sousa Malafaia, Mater. Res. 20 (2017) 365-373.
[63]	J.H. Chen, P.M. Rogers, J.A. Little, Oxid. Met. 47 (1997) 381-410. DOI URL