Enhancing the Corrosion Resistance of FeNiCoCrW0.2Al0.1 High-Entropy Alloy in 3.5 wt% NaCl Solution by Bilayer Passivation

doi:10.1007/s40195-024-01804-y

Abstract

Abstract:

The strong corrosion resistance and corrosion behavior of the FeNiCoCrW_0.2Al_0.1 high-entropy alloy in 3.5 wt% NaCl solution was investigated. In order to explain the Cl⁻ induced degradation of different metal oxides on the surface of the passivate film, the energy required for the interaction of the corrosion oxidation products NiO, CoO, Fe₂O₃, and Cr₂O₃ surfaces with Cl⁻ is compared and calculated based on the assumptions of the point defect model and the density functional theory by using the electrochemical impedance spectroscopy and the X-ray photoelectron spectroscopy for the analysis of the mono-double-layer structure and elemental compositions of passivate film in the corrosion process. The combined experimental and simulation results showed that the alloy passivates naturally in air, forming a single passivation layer. The compositional layering of the passivation film in 3.5 wt% NaCl solution occurred with the increase of the contact time with NaCl. A double-layer passivation with a two-layered combinatorial structure was formed due to the imbalanced depletion of Co and Fe during corrosion, and that the dense outer structure of this high-entropy alloy, which was made up of NiO and Cr₂O₃, provided the predominantly high corrosion resistance. This paper provided a new perspective to study the strong corrosion resistance of FeNiCoCr-based high-entropy alloys.

Key words: High-entropy alloys, Passivation films, Corrosion, Density functional theory

Jingxiang Xu, Yuyan Yang, Ruiyang Huang, Xinwei Yuan, Huakang Bian, Zhenhua Chu, Yang Wang, Yanhua Lei. Enhancing the Corrosion Resistance of FeNiCoCrW_0.2Al_0.1 High-Entropy Alloy in 3.5 wt% NaCl Solution by Bilayer Passivation[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(3): 407-418.

Figures/Tables 15

References 39

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	K-points	Cutoff energy (eV)	Force convergence (eV/Å)	Magnetic mom (μ)	U	J
CoO (111)	4 × 4 × 1	480	0.01	1.90 (Ref. [36])	3.70 (Ref. [36])	0 (Ref. [36])
(3 × 3)	4 × 4 × 1	480	0.01	1.90 (Ref. [36])	3.70 (Ref. [36])	0 (Ref. [36])
NiO (111)	4 × 4 × 1	480	0.01	2.90 (Ref. [24])	6.30 (Ref. [24])	0 (Ref. [24])
(3 × 3)	4 × 4 × 1	480	0.01	2.90 (Ref. [24])	6.30 (Ref. [24])	0 (Ref. [24])
α-Fe₂O₃ (0001)	3 × 3 × 1	480	0.01	4.90 (Ref. [27])	4.00 (Ref. [27])	0 (Ref. [27])
(2 × 2)	3 × 3 × 1	480	0.01	4.90 (Ref. [27])	4.00 (Ref. [27])	0 (Ref. [27])
α-Cr₂O₃ (0001)	3 × 3 × 1	480	0.01	3.05 (Ref. [26])	5.00 (Ref. [26])	1.00 (Ref. [26])
(2 × 2)	3 × 3 × 1	480	0.01	3.05 (Ref. [26])	5.00 (Ref. [26])	1.00 (Ref. [26])

	K-points	Cutoff energy (eV)	Force convergence (eV/Å)	Magnetic mom (μ)	U	J
CoO (111)	4 × 4 × 1	480	0.01	1.90 (Ref. [36])	3.70 (Ref. [36])	0 (Ref. [36])
(3 × 3)	4 × 4 × 1	480	0.01	1.90 (Ref. [36])	3.70 (Ref. [36])	0 (Ref. [36])
NiO (111)	4 × 4 × 1	480	0.01	2.90 (Ref. [24])	6.30 (Ref. [24])	0 (Ref. [24])
(3 × 3)	4 × 4 × 1	480	0.01	2.90 (Ref. [24])	6.30 (Ref. [24])	0 (Ref. [24])
α-Fe₂O₃ (0001)	3 × 3 × 1	480	0.01	4.90 (Ref. [27])	4.00 (Ref. [27])	0 (Ref. [27])
(2 × 2)	3 × 3 × 1	480	0.01	4.90 (Ref. [27])	4.00 (Ref. [27])	0 (Ref. [27])
α-Cr₂O₃ (0001)	3 × 3 × 1	480	0.01	3.05 (Ref. [26])	5.00 (Ref. [26])	1.00 (Ref. [26])
(2 × 2)	3 × 3 × 1	480	0.01	3.05 (Ref. [26])	5.00 (Ref. [26])	1.00 (Ref. [26])

Alloy composition	E_corr (mV)	i_corr (A/cm²)	References
FeCoNiCr_0.5	− 319	2.36 × 10^-6	[6]
CoCrFeNiGe_0.3	− 34	5.60 × 10^-5	[7]
Al₂CrFeCoCuTiNi	− 220	1.30 × 10^-4	[8]
Al₂CrFeCoCuTiNi₂	− 500	6.70 × 10^-4	[8]
Al_0.9CoCrFeNiTi_0.5	− 347	3.10 × 10^-8	[9]
CoCrFeNi₂Mo_0.25	− 260	1.25 × 10^-7	[10]
CoCrFeNiMo_0.4	− 261	8.20 × 10^-8	[11]
Al_0.3CoCrFeNi	− 195	8.40 × 10^-8	[12]
(CoCrFeNi)₉₅Nb₅	− 128	7.23 × 10^-6	[13]
Co₂CrCuFeMnNi	− 787	6.95 × 10^-6	[14]
FeCoCrNiW_0.2Al_0.1	− 163 ± 14	(2.24 ± 0.09) × 10^-7	Present work

Alloy composition	E_corr (mV)	i_corr (A/cm²)	References
FeCoNiCr_0.5	− 319	2.36 × 10^-6	[6]
CoCrFeNiGe_0.3	− 34	5.60 × 10^-5	[7]
Al₂CrFeCoCuTiNi	− 220	1.30 × 10^-4	[8]
Al₂CrFeCoCuTiNi₂	− 500	6.70 × 10^-4	[8]
Al_0.9CoCrFeNiTi_0.5	− 347	3.10 × 10^-8	[9]
CoCrFeNi₂Mo_0.25	− 260	1.25 × 10^-7	[10]
CoCrFeNiMo_0.4	− 261	8.20 × 10^-8	[11]
Al_0.3CoCrFeNi	− 195	8.40 × 10^-8	[12]
(CoCrFeNi)₉₅Nb₅	− 128	7.23 × 10^-6	[13]
Co₂CrCuFeMnNi	− 787	6.95 × 10^-6	[14]
FeCoCrNiW_0.2Al_0.1	− 163 ± 14	(2.24 ± 0.09) × 10^-7	Present work

	R_s (Ω cm²)	R_ct (Ω cm²)	R_pas (Ω cm²)	R_pas1 (Ω cm²)	R_pas2 (Ω cm²)	CPE_dl (S sⁿ cm⁻²)	n_dl	CPE_pas (S sⁿ cm⁻²)	n_pas	CPE_pas1 (S sⁿ cm⁻²)	n_pas1	CPE_pas2 (S sⁿ cm⁻²)	n_pas2	d_pas (nm)	d_pas1 (nm)	d_pas2 (nm)
0 d	10.45	1.81 × 10⁴	1.18 × 10⁴	-	-	1.01 × 10^-4	0.91	3.73 × 10^-5	0.94	-		-		7.12	-	-
9 d	7.47	-	-	630	2430	-		-		5.05 × 10^-5	0.84	2.56 × 10^-4	0.73	-	5.26	1.04
24 d	7.27	-	-	1702	1310	-		-		6.25 × 10^-5	0.8	8.07 × 10^-5	0.8	-	4.25	3.29