Effect of nitrogen on corrosion behaviour of a novel high nitrogen medium-entropy alloy CrCoNiN manufactured by pressurized metallurgy

doi:10.1016/j.jmst.2018.03.021

摘要/Abstract

Abstract:

A novel high nitrogen medium-entropy alloy CrCoNiN, which had higher strength and slightly lower ductility than CrCoNi alloy, was successfully manufactured by pressurized metallurgy. The microstructure and corrosion behaviour were investigated by microscopic, electrochemical and spectroscopic methods. The results indicated that nitrogen existed in the form of Cr₂N precipitates and uniformly distributed N atoms, and nitrogen alloying significantly refined the grain size. Besides, nitrogen enriched on the outmost surface of passive film and metal/film interface as ammonia (NH₃ and NH4+) and CrN, respectively. The significant improvement of corrosion resistance of CrCoNiN was attributed to the lower metastable pitting susceptibility together with thicker, less defective and more compact passive film.

Key words: Medium-entropy alloy, Nitrogen, Pitting corrosion, Passive film, Metastable pitting

. [J]. 材料科学与技术, 2018, 34(10): 1781-1790.

Hao Feng, Huabing Li, Xiaolei Wu, Zhouhua Jiang, Si Zhao, Tao Zhang, Dake Xu, Shucai Zhang, Hongchun Zhu, Binbin Zhang, Muxin Yang. Effect of nitrogen on corrosion behaviour of a novel high nitrogen medium-entropy alloy CrCoNiN manufactured by pressurized metallurgy[J]. J. Mater. Sci. Technol., 2018, 34(10): 1781-1790.

图/表 16

Table 1 Chemical compositions and mechanical properties of the investigated medium-entropy alloys.

	Chemical composition					Mechanical properties (at 25 °C)
Alloys		Cr	Co	Ni	N	Yield strength (MPa)	Ultimate tensile strength (MPa)	Elongation (%)
CrCoNi	wt%	30.58	34.71	34.71	-	205.6	638.6	68.9
CrCoNi	at%	33.25	33.31	33.44	-	205.6	638.6	68.9
CrCoNiN	wt%	30.45	34.56	34.55	0.44	374.4	1161.1	43.0
CrCoNiN	at%	32.68	32.73	32.84	1.75	374.4	1161.1	43.0

Fig. 1. OM, SEM and TEM micrographs of (a), (c), (e) CrCoNi and (b), (d), (f) CrCoNiN medium-entropy alloys.

Fig. 2. 3D atom-by-atom tomographic reconstruction (box size 87 nm × 87 nm × 216 nm) of CrCoNiN medium-entropy alloy.

Fig. 3. Potentiodynamic polarization curves and cyclic polarization curves of (a)(c) CrCoNi and (b)(d) CrCoNiN medium-entropy alloys.

Table 2 Potentiodynamic and cyclic polarization parameters of the investigated medium-entropy alloys.

Alloys	Temperature (°C)	Potentiodynamic polarization		Cyclic polarization
Alloys	Temperature (°C)	I_corr × 10⁷ (A/cm²)	E_pit (mV_SCE)	E_pit (mV_SCE)	E_rp (mV_SCE)	I_max (mA/cm²)
CrCoNi	30	1.40 ± 0.33	744.9 ± 2.6	762.8 ± 2.2	E_pit	1.1 ± 0.0
	50	2.85 ± 0.34	336.7 ± 24.6	421.3 ± 8.1	147.3 ± 19.2	3.4 ± 0.2
	70	3.18 ± 0.96	240.7 ± 16.1	270.0 ± 10.5	55.3 ± 6.8	3.6 ± 0.9
CrCoNiN	30	1.39 ± 0.35	782.4 ± 9.7	763.1 ± 1.3	E_pit	1.0 ± 0.0
	50	2.34 ± 0.44	712.0 ± 8.7	711.6 ± 4.0	E_pit	1.0 ± 0.0
	70	2.75 ± 0.77	663.4 ± 35.1	660.9 ± 0.8	E_pit	1.0 ± 0.0

Fig. 4. Typical potentiostatic curves of CrCoNi and CrCoNiN medium-entropy alloys at 600 mVSCE in 3.5 wt% NaCl solution.

Table 3 Main alloying element contents and CPT values of commercial stainless steels in literatures.

Alloys	Contents of main alloying elements (wt%)				CPT (°C)	Testing solutions
Alloys	Cr	Mo	N	Ni	CPT (°C)	Testing solutions
304 [34]	18	/	/	9	4.6	1 M NaCl
316L [30]	17.13	2.15	/	12.7	17.2	3.5 wt% NaCl
904L [35]	20.06	4.32	/	25.04	51.1	1 M NaCl
2101DSS [36]	21.4	0.31	0.23	1.2	33	1 M NaCl
2304DSS [37]	23.23	0.42	0.12	4.8	33	1 M NaCl

Fig. 5. (a) Mott-Schottky plots and (b) acceptor densities for passive films on CrCoNi and CrCoNiN medium-entropy alloys.

Fig. 6. (a) XPS spectra, (b) ratios of Cr/(Cr+Ni+Co) and (c) contents of O 1 s in the passive films on CrCoNi and CrCoNiN medium-entropy alloys.

Fig. 7. XPS spectra of Cr 2p3/2, Co 2p3/2, Ni 2p3/2 and O 1 s recorded from the outmost surface of passive films on (a) CrCoNi and (b) CrCoNiN medium-entropy alloys.

Fig. 8. XPS spectra of N 1 s recorded from the sputtering surfaces for (a) 0 s, (b) 10 s, (c) 70 s and (d) 170 s of the passive film on CrCoNiN medium-entropy alloy.

Table 4 Contents of Ni, Co and Cr elements in the passive films on medium-entropy alloys (at%).

Elements	Alloys	Etching time (s)
Elements	Alloys	0	10	20	30
Ni	CrCoNi	5.75	25.06	31.66	31.14
	CrCoNiN	7.74	17.28	26.49	32.53
Co	CrCoNi	4.51	21.85	29.26	33.92
	CrCoNiN	3.24	13.20	18.36	24.28
Cr	CrCoNi	8.24	21.02	18.03	16.36
	CrCoNiN	8.44	23.92	23.10	19.36

Fig. 9. Peak areas of species in (a) Cr 2p3/2 in the passive films on CrCoNi and CrCoNiN medium-entropy alloys and (b) N 1 s in the passive films on CrCoNiN alloy.

Fig. 10. Schematic diagram of physicochemical processes based on PDM model. m = metal atom, VMx′ = cation vacancy, MM = metal cation in cation site, Vm = vacancy in metal site, Mix+ = cation interstitial, VO¨ = oxygen vacancy, Mδ+ (aq) = metal cation in electrolyte, OO = oxygen ion in anion site, Cl- (aq) = chloride ion in electrolyte, Clo˙ = oxygen vacancy occupied by Cl-, N = nitrogen atom, N? = nitrogen ion.

Fig. 11. Morphologies of pitting initiation sites of CrCoNi and CrCoNiN medium-entropy alloys.

Fig. 12. Schematic diagrams of corrosion mechanism of (a) CrCoNi and (b) CrCoNiN medium-entropy alloys.

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