Dissolution and repair of passive film on Cu-bearing 304L stainless steels immersed in H2SO4 solution

doi:10.1016/j.jmst.2018.02.017

Abstract

Abstract:

The antibacterial Cu-bearing 304L stainless steel is a new kind of structural and functional integrated metal material. In this work, evolution behavior of passive film of different heat treated Cu-bearing 304L stainless steel immersed in 0.5 M H₂SO₄ solution was investigated by using electrochemical measurements, atomic force microscopy (AFM) observation and X-ray photoelectron spectroscopy (XPS) analysis. The results show that the solution and aging treated samples have the similar polarization behaviors. The passive film impedance experiences an initial decrease within 7 days followed by a subsequent increase, while the defect density of passive film presents the opposite trend. Meanwhile, the evolution of surface morphology and the estimated thickness of the passive film confirm that it experiences initial dissolution and follow-up repair. Furthermore, the Cr³⁺ content in passive film undergoes sequential reduction to increase, however the variation tendency of Cu²⁺ content is just opposite, indicating that the content variation of Cr and Cu in passive film reflects the competitive process of film dissolution and repair. In addition, compared with solution treated samples, aged samples have a bigger i_corr value and the rougher passive film. This indicates that the passive film of solution treated steel is more compact and stable.

Key words: Cu-bearing stainless steel, 304L-Cu, Passive film

Xinrui Zhang, Jinlong Zhao, Tong Xi, M. Babar Shahzad, Chunguang Yang, Ke Yang. Dissolution and repair of passive film on Cu-bearing 304L stainless steels immersed in H₂SO₄ solution[J]. J. Mater. Sci. Technol., 2018, 34(11): 2149-2159.

Figures/Tables 14

Fig. 1. Potentiodynamic polarization curves of solution and aging treated 304L-Cu SSs.

Fig. 2. Electrochemical impedance diagrams of solution ((a) Nyquist and (b) Bode plots) and aging ((c) Nyquist and (d) Bode plots) treated 304L-Cu SSs after immersion in 0.5 M H2SO4 for different time.

Fig. 3. Equivalent circuit used to fit the impedance spectra of 304L-Cu SSs.

Table 1 Fitted corrosion parameters from EIS tests for the solution and aging treated 304L-Cu SS immersion in 0.5 M H2SO4 for different time.

Heat treatments	Immersion time (day)	R_s (Ω cm²)	Q_f × 10^-5 (Ω^-1 cm^-2)	n_f	R_f (kΩ cm²)	Q_dl × 10^-5 (Ω^-1 cm^-2)	n_dl	R_ct (kΩ cm²)
Solution	0	2.34	5.72	0.97	307.62	3.49	0.87	513.72
	2	2.53	5.41	0.91	271.53	2.50	0.85	424.15
	7	2.51	5.35	0.90	47.90	1.96	0.85	61.01
	12	2.51	5.61	0.90	56.73	2.81	0.60	389.13
	14	2.52	5.37	0.90	62.68	3.25	0.60	462.77
Aging	0	2.11	4.37	0.91	62.75	1.65	0.70	246.83
	2	1.90	4.04	0.91	21.65	1.62	0.61	165.51
	7	1.43	4.43	0.90	13.09	2.70	0.68	56.13
	12	2.57	4.41	0.88	13.67	1.72	0.52	148.56
	14	1.67	3.99	0.91	14.86	1.20	0.53	221.34

Fig. 4. Mott-Schottky curves of 304L-Cu SSs treated by (a) solution (b) aging after immersion in 0.5 M H2SO4 for different time.

Table 2 Charge carrier density of solution and aging treated 304L-Cu SS after immersion in 0.5 M H2SO4 for different time.

Heat treatments	Immersion time (day)	Donor density, N_D (cm^-3)	Acceptor density, N_A (cm^-3)
Solution	0	3.14 × 10²¹	8.44 × 10²¹
	2	3.78 × 10²¹	9.37 × 10²¹
	7	8.08 × 10²¹	9.80 × 10²¹
	12	5.32 × 10²¹	6.03 × 10²¹
	14	4.98 × 10²¹	5.13 × 10²¹
Aging	0	3.71 × 10²¹	8.68 × 10²¹
	2	4.03 × 10²¹	9.70 × 10²¹
	7	9.18 × 10²¹	9.88 × 10²¹
	12	6.86 × 10²¹	7.50 × 10²¹
	14	5.82 × 10²¹	7.48 × 10²¹

Fig. 5. AFM images for the passive film of solution (a, b, c) and aging (d, e, f) treated 304L-Cu SSs after immersion in 0.5 M H2SO4 for different time: (a, d) 0 day, (b, e) 7 days, (c, f) 14 days.

Table 3 Calculated root mean square roughness (Rq) for the solution and aging treated 304L-Cu SS immersed in 0.5 M H2SO4 for different time.

Heat treatments	Immersion time (day)	R_q(nm)
Solution	0	6.61
	7	9.50
	14	6.05
Aging	0	7.33
	7	11.17
	14	7.68

Fig. 6. XPS spectra of Cr 2p and Cu 2p detected in the passive film of solution treated 304L-Cu SSs after immersion in 0.5 M H2SO4 for different time: (a, d) 0 day, (b, e) 7 days, (c, f) 14 days.

Fig. 7. XPS spectra of Cr 2p and Cu 2p detected in the passive film of aged 304L-Cu SSs after immersion in 0.5 M H2SO4 for different time: (a, d) 0 day, (b, e) 7 days, (c, f) 14 days.

Table 4 Parameters for decomposition of Cr 2p and Cu 2p spectra for the solution and aging treated 304L-Cu SS after immersion in 0.5 M H2SO4 for different time.

Heat treatments	Immersion time (day)	Cr³⁺ (at.%)	Cu (at.%)	CuO (at.%)
Solution	0	11.77	2.27	0.77
	7	7.73	2.70	3.38
	14	12.24	1.99	2.42
Aging	0	10.21	3.17	0.61
	7	4.74	4.00	4.67
	14	10.66	2.30	2.83

Fig. 8. Composition depth profiles of passive films of solution (a, b, c) and aging (d, e, f) treated 304L-Cu SSs after immersion in 0.5 M H2SO4 for different time: (a, d) 0 day, (b, e) 7 days, (c, f) 14 days.

Table 5 Estimated thicknesses of passive film for the solution and aging treated 304L-Cu SS after immersion in 0.5 M H2SO4 for different time.

Heat treatments	Immersion time (day)	Thickness(nm)
Solution	0	4.95
	7	1.15
	14	1.45
Aging	0	3.98
	7	0.70
	14	1.18

Fig. 9. Schematic diagrams of evolution process of passive film during immersion in 0.5 M H2SO4 for 14 days: (a) 0 day, (b) 0-7 days, (c) 7-14 days.

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Dissolution and repair of passive film on Cu-bearing 304L stainless steels immersed in H₂SO₄ solution

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