Corrosion Behaviour of a Non-equiatomic CoCrFeNiMo High-Entropy Alloy in H2S-Containing and H2S-Free Environments

doi:10.1007/s40195-022-01466-8

Abstract

Abstract:

The corrosion behaviour of a non-equiatomic CoCrFeNiMo high-entropy alloy (HEA) in H₂S-containing and H₂S-free environments was studied by electrochemical tests, surface characterization, and solution analysis. The results showed that the HEA exhibited primary and secondary passivation in the H₂S-free environment, and the transition was owing to the enhanced dissolution of Fe species. Compared with the primary passive film, the Cr/Fe ratio in the secondary passive film increased at the expense of the selective dissolution of Fe. Therefore, the corrosion resistance of HEA decreased with the applied potential. Cr was the most stable element in the film of HEA, regardless of H₂S. The presence of H₂S accelerated the dissolution of all the cationic elements in the HEA. H₂S promoted the formation of thicker but less protective surface film and induced the loss of passivity.

Key words: High-entropy alloy (HEA), Corrosion, H₂S, Secondary passivation, X-ray photoelectron spectroscopy (XPS), Induced coupled plasma (ICP)

Zhu Wang, Guo-Hui Zhang, Yong Yao, Xue-Hua Fan, Jie Jin, Lei Zhang, Yan-Xia Du. Corrosion Behaviour of a Non-equiatomic CoCrFeNiMo High-Entropy Alloy in H₂S-Containing and H₂S-Free Environments[J]. Acta Metallurgica Sinica (English Letters), 2023, 36(3): 366-378.

Figures/Tables 13

Table 1 Chemical composition of the HEA (at.%)

Co	Cr	Fe	Ni	Mo
26.8	24.3	24.5	24.2	0.3

Fig. 1 XRD pattern of the HEA used in this study

Fig. 2 Polarization curves of the HEA in the test solution with or without H2S

Fig. 3 Impedance spectra of the HEA measured at OCPs in the test solution in H2S-free and H2S-containing environments: a Nyquist plots, b Bode plots

Fig. 4 Equivalent circuit used in this study

Table 2 Values of the equivalent circuit elements

Condition	R_s	Q_f × 10⁵	n_f	R_f	δ
Condition	(Ω cm²)	(Ω⁻¹ cm⁻² sⁿ)		(kΩ cm²)	(nm)
N₂	10.5	5.99	0.88	461	2.8
H₂S	10.6	8.95	0.75	49.4	27.2

Fig. 5 Mott-Schottky plots for the HEA in the test solution

Fig. 6 Potentiostatic polarization curves of the HEA at various applied potentials in a H2S-free and b H2S-containing environments

Fig. 7 High-resolution XPS spectra obtained on the HEA in H2S-free environment: a Cr 2p3/2, b Fe 2p3/2, c Co 2p3/2 d Ni 2p3/2, e Mo 3d, f O 1 s

Fig. 8 High-resolution XPS spectra obtained on the HEA in H2S-containing environment: a Cr 2p3/2, b Fe 2p3/2, c Co 2p3/2, d Ni 2p3/2, e Mo 3d, f O 1 s, g S 2p

Table 3 Concentrations of Co, Cr, Fe, Ni, and Mo released in the test solutions

Condition		Concentration (10⁻⁶ mol L⁻¹)
Gas	Potential (V, SCE)	Co	Cr	Fe	Ni	Mo
N₂	− 0.36	0.87	0.13	0.61	0.94	0.01
	− 0.20	1.46	0.15	1.15	1.52	0.01
	0.05	1.60	0.21	2.44	2.27	0.02
	0.33	390.8	404.6	397.4	380.5	4.10
H₂S	− 0.36	1.05	0.40	1.34	0.95	0.01
	− 0.20	2.56	1.17	3.64	2.30	0.04
	0.05	1522	1453	1481	1380	17.5

Fig. 9 Selective coefficients of Co, Cr, Fe, Ni, and Mo in the a H2S-free environment and b H2S-containing environment

Fig. 10 Fractions of the main components in the films of HEA formed in the a H2S-free environments and b H2S-containing environments

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Corrosion Behaviour of a Non-equiatomic CoCrFeNiMo High-Entropy Alloy in H₂S-Containing and H₂S-Free Environments

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