Cl-induced passivity breakdown in α-Fe2O3 (0001), α-Cr2O3 (0001), and their interface: A DFT study

doi:10.1016/j.jmst.2022.03.034

Abstract

Abstract:

The presence of chloride ions is the critical factor of passivity breakdown of the protective film and eventually leads to localized corrosion. However, the mechanism and the role of chlorides in these processes are still controversial. Hematite and chromia are generally believed to be the major components of outer and inner oxide layers on stainless steels. In the present paper, a comparative study of Cl ingress into pristine and defective α-Fe₂O₃ (0001) surface, α-Cr₂O₃ (0001) surface, along with their interface, was conducted using density functional theory. Vacancy formation energy calculation confirms good stability of α-Cr₂O₃ and high reactive activity of the interface region. Cl inserts into an O vacancy is energetically more favorable than Fe vacancy and interstitial site, demonstrating Cl-induced degradation complies with the ion exchange model. Transition state search for Cl diffusion through O vacancies shows α-Cr₂O₃ is more protective than α-Fe₂O₃, while the interface region is the weak point of the duplex passive film.

Key words: Hematite, Chromia, DFT+U, Interface, Cl-induced depassivation

Xiaoran Yin, Haitao Wang, En-Hou Han. Cl-induced passivity breakdown in α-Fe₂O₃ (0001), α-Cr₂O₃ (0001), and their interface: A DFT study[J]. J. Mater. Sci. Technol., 2022, 129: 70-78.

Figures/Tables 13

Fig. 1. Crystal structure and projected density of states (PDOS) of (a) α-Fe2O3 and (b) α-Cr2O3 bulk. The most favorable spin arrangements are also shown.

Table 1. Physical properties of α-Fe2O3 and α-Cr2O3.

	Lattice parameter, a (Å)	Lattice parameter, c (Å)	Magnetic moment, μ_B	Bandgap, E_g (eV)
Fe₂O₃	5.074, 5.027^a, 5.035^b	13.891, 13.724^a, 13.67^b	4.15, 4.2^c	2.12, 2.1^c
Cr₂O₃	5.073, 5.06^d, 5.05^e	13.840, 13.92^d, 13.86^e	3.02, 3.05^d, 3.10^e	2.83, 2.86^d, 2.89^e

Fig. 2. Interplanar relaxation for (a) α-Fe2O3 (0001) and (b) α-Cr2O3 (0001) surfaces. Experimental and theoretical data are given for comparison.

Fig. 3. O vacancy formation energy in α-Fe2O3 (0001) and α-Cr2O3 (0001) surfaces.

Fig. 4. Cation vacancy formation energy in α-Fe2O3 (0001) and α-Cr2O3 (0001) surfaces.

Fig. 5. PDOS for α-Fe2O3 (0001) and α-Cr2O3 (0001) surfaces. (a, d) Perfect surface. (b, e) Cation vacancy surface. (c, f) O vacancy surface.

Fig. 6. Insertion energy of Cl in different interstitial sites at α-Fe2O3 (0001) and α-Cr2O3 (0001) surfaces.

Fig. 7. Insertion energy of Cl in different vacancy sites at α-Fe2O3 (0001) and α-Cr2O3 (0001) surfaces.

Table 2. Energy barriers ($\text{ }\!\!\Delta\!\!\text{ }{{E}_{n-n+1}}$, eV) for Cl interlayer diffusion through O vacancies.

	$\text{ }\!\!\Delta\!\!\text{ }{{E}_{1-2}}$	$\text{ }\!\!\Delta\!\!\text{ }{{E}_{2-3}}$	$\text{ }\!\!\Delta\!\!\text{ }{{E}_{3-4}}$
α-Fe₂O₃(0001)	2.31	1.54	1.30
α-Cr₂O₃(0001)	3.50	2.01	1.52

Fig. 8. α-Fe2O3/α-Cr2O3 (0001) interface structures for the (a) oxygen-divided (OD) and (b) split-metal (SM) interfaces. The Fe, Cr, and O ions are marked with brown, blue, and red disks, respectively.

Fig. 9. Electronic properties (a) 3D charge density difference (isovalue: 0.004 eV/?3), (b) plane-averaged charge density difference along z-direction, and (c) projected density of states of α-Fe2O3/α-Cr2O3 (0001) interface.

Fig. 10. Schematic diagram of (a) in-plane and (b) cross-plane diffusion paths for O or Cl diffusion through O vacancies at the interface. In the figure, red, brown and blue balls represent O, Fe and Cr atoms, respectively. Green balls represent the migrating O or Cl ion. The diffusion paths are shown by black arrows.

Fig. 11. Comparison of the energy barriers for O and Cl diffusion in α-Fe2O3 (0001), α-Cr2O3 (0001), and their interface region.

References 53

[1]	J.M. Cordeiro, B.E. Nagay, M.T. Mathew, V.A.R. Barao, R. Inamuddin, et al., Alloy Materials and Their Allied Applications, John Wiley & Sons, Inc., New Jersey, 2020.
[2]	N.E. Hakiki, Corros. Sci. 53 (2011) 2688-2699. DOI URL
[3]	K.B. Fisher, B.D. Miller, E.C. Johns, E.A. Marquis, Corros. Sci. 141 (2018) 88-96. DOI URL
[4]	L.T. Wang, A. Seyeux, P. Marcus, Corros. Sci. 165 (2020) 108395. DOI URL
[5]	H.T. Zeng, Y. Yang, M.H. Zeng, M.C. Li, J. Mater. Sci. Technol. 66 (2021) 177-185. DOI URL
[6]	D. Ramachandran, R. Egoavil, A. Crabbe, T.O.M. Hauffman, A. Abakumov, J. Ver- beeck, I. Vandendael, H. Terryn, D. Schryvers, J. Microsc. 264 (2016) 207-214. DOI URL
[7]	L. Ma, F. Wiame, V. Maurice, P. Marcus, Appl. Surf. Sci. 494 (2019) 8-12. DOI URL
[8]	T. Li, J. Scully, G. Frankel, J. Electrochem. Soc. 165 (2018) C762-C770.
[9]	P.M. Natishan, W.E. O’Grady, F. Martin, R.J. Rayne, H. Kahn, A.H. Heuer, J. Elec- trochem. Soc. 158 (2011) C7-C10.
[10]	S.F. Deng, S.B. Wang, L.Y. Wang, J.T. Liu, Y.J. Wang, Int. J. Electrochem. Sci. 12 (2017) 1106-1117.
[11]	S.A. Saadi, Y.S. Yi, P. Cho, C. Jang, P. Beeley, Corros. Sci. 111 (2016) 720-727. DOI URL
[12]	Y.F. Lu, J.H. Dong, W. Ke, J. Mater. Sci. Technol. 32 (2016) 341-348. DOI URL
[13]	B. Zhang, X.X. Wei, B. Wu, J. Wang, X.H. Shao, L.X. Yang, S.J. Zheng, Y.T. Zhou, Q.Q. Jin, E.E. Oguzie, X.L. Ma, Corros. Sci. 154 (2019) 123-128. DOI
[14]	J. Soltis, Corros. Sci. 90 (2015) 5-22. DOI URL
[15]	T.P. Hoar, D.C. Mears, G.P. Rothwell, Corros. Sci. 5 (1965) 279-289. DOI URL
[16]	D.D. Macdonald, J. Electrochem. Soc. 139 (1992) 3434-3449. DOI URL
[17]	D.D. Macdonald, Electrochim. Acta 56 (2011) 1761-1772. DOI URL
[18]	Y.H. Li, D.D. Macdonald, J. Yang, J. Qiu, S.Z. Wang, Corros. Sci. 163 (2020) 108280. DOI URL
[19]	Y.W. Cui, L.Y. Chen, X.X. Liu, Curr. Nanosci. 17 (2021) 241-256. DOI URL
[20]	N. Sato, S.K. Sharma, Green Corrosion Chemistry and Engineering:Opportuni- ties and Challenges, John Wiley & Sons, Inc., New Jersey, 2011.
[21]	B. Zhang, J. Wang, B. Wu, X.W. Guo, Y.J. Wang, D. Chen, Y.C. Zhang, K. Du, E.E. Oguzie, X.L. Ma, Nat. Commun. 9 (2018) 2559. DOI PMID
[22]	M. Liu, Y. Jin, C. Leygraf, J. Pan, J. Electrochem. Soc. 166 (2019) C3124-C3130.
[23]	A. Bouzoubaa, B. Diawara, V. Maurice, C. Minot, P. Marcus, Corros. Sci. 51 (2009) 941-948. DOI URL
[24]	K. Oware Sarfo, P. Murkute, O.B. Isgor, Y. Zhang, J. Tucker, L. Árnadóttir, J. Elec- trochem. Soc. 167 (2020) 121508.
[25]	Q. Pang, H. DorMohammadi, O.B. Isgor, L. Árnadóttir, Corros. Sci. 154 (2019) 61-69. DOI
[26]	G. Kresse, J. Furthmüller, Phys. Rev. B 54 (1996) 11169-11186. DOI PMID
[27]	G. Kresse, J. Furthmüller, Comput. Mater. Sci. 6 (1996) 15-50. DOI URL
[28]	J. Hafner, J. Comput. Chem. 29 (2008) 2044-2078. DOI URL
[29]	J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865-3868. DOI PMID
[30]	Z.H. Yang, J.W. Sun, J. Perdew, Phys. Rev. B 93 (2016) 205205. DOI URL
[31]	P.E. Blöchl, Phys. Rev. B 50 (1994) 17953-17979. DOI URL
[32]	S. Dudarev, G.A. Botton, S.Y. Savrasov, C. Humphreys, A.P. Sutton, Phys. Rev. B 57 (1998) 1505-1509. DOI URL
[33]	Q. Pang, H. DorMohammadi, O.B. Isgor, L. Árnadóttir, Comput. Theor. Chem. 1100 (2017) 91-101. DOI URL
[34]	H.J. Monkhorst, J.D. Pack, Phys. Rev. B 13 (1976) 5188-5192. DOI URL
[35]	G. Henkelman, B.P. Uberuaga, H. Jónsson, J. Chem. Phys. 113 (2000) 9901-9904.
[36]	S.A. Fuente, L.F. Fortunato, C. Zubieta, R.M. Ferullo, P.G. Belelli, Mol. Catal. 446 (2018) 10-22.
[37]	Z.S. Mi, L. Chen, C.M. Shi, L. Gao, D.C. Wang, X.L. Li, H.M. Liu, L.J. Qiao, Appl. Surf. Sci. 475 (2019) 294-301. DOI URL
[38]	R. Ivantsov, O. Ivanova, S. Zharkov, M. Molokeev, A. Krylov, I. Gudim, I. Edel- man, J. Magn. Magn. Mater. 498 (2020) 166208. DOI URL
[39]	T. Lino, T. Moriyama, H. Lwaki, H. Aono, Y. Shiratsuchi, T. Ono, Appl. Phys. Lett. 114 (2019) 022402. DOI URL
[40]	B. Gilbert, C. Frandsen, E. Maxey, D. Sherman, Phys. Rev. B 79 (2009) 035108. 1-035108.7. DOI URL
[41]	A.K. Vijh, Corros. Sci. 12 (1972) 105-111. DOI URL
[42]	R. Ovcharenko, E. Voloshina, J. Sauer, Phys. Chem. Chem. Phys. 18 (2016) 25560-25568. PMID
[43]	C. Gray, Y. Lei, G. Wang, J. Appl. Phys. 120 (2016) 215101. DOI URL
[44]	M.T. Nguyen, N. Seriani, R. Gebauer, ChemPhysChem 15 (2014) 2930-2935. DOI URL
[45]	T. Pabisiak, A. Kiejna, J. Phys. Commun. 3 (2019) 035023. DOI URL
[46]	A. Rohrbach, J. Hafner, G. Kresse, Phys. Rev. B 70 (2004) 125426. DOI URL
[47]	T. Stirner, D. Scholz, J. Sun, Surf. Sci. 671 (2018) 11-16. DOI URL
[48]	J. Sun, T. Stirner, A. Matthews, Surf. Coat. Technol. 201 (2006) 4205-4208. DOI URL
[49]	A. Mahmoud, P.M. Deleuze, C. Dupont, J. Chem. Phys. 148 (2018) 204701. DOI URL
[50]	M. Bender, D. Ehrlich, I.N. Yakovkin, F. Rohr, M. Baumer, H. Kuhlenbeck, H.J. Freund, V. Staemmler, J. Phys. Condens. Matter 7 (1995) 5289-5301. DOI URL
[51]	M.M. Waegele, H.Q. Doan, T. Cuk, J. Phys. Chem. C 118 (2014) 3426-3432.
[52]	J. Lee, S. Han, Phys. Chem. Chem. Phys. 15 (2013) 18906-18914. DOI URL
[53]	P.P. Zhao, Y.W. Song, L.J. Shi, K.H. Dong, D.Y. Shan, E.H. Han, J. Mater. Sci. 56 (2021) 3510-3524. DOI URL

Cl-induced passivity breakdown in α-Fe₂O₃ (0001), α-Cr₂O₃ (0001), and their interface: A DFT study

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