Passivation Behavior of 2507 Super Duplex Stainless Steel in Hot Concentrated Seawater: Influence of Temperature and Seawater Concentration

doi:10.1007/s40195-021-01272-8

Abstract

Abstract:

The electrochemical behavior and passivation properties of 2507 super duplex stainless steel (SDSS) in the hot concentrated seawater with different concentrations at different temperatures are characterized by electrochemical methods and X-ray photoelectron spectroscopy. The passive film formed on 2507 SDSS belongs to n-type semiconductor and mainly composed of hydroxides and oxides of Fe and Cr under all circumstances. The protectiveness of the passive film decreases with the increase in temperature mainly because of the increase in defect density in the passive film. The corrosion resistance of 2507 decreases with the increase in seawater concentration, and the critical pitting temperature also decreases.

Key words: Stainless steel, Hot concentrated seawater, Passive film, Pitting

Kang Zhao, Xiao-Qi Li, Li-Wei Wang, Qi-Rong Yang, Lian-Jun Cheng, Zhong-Yu Cui. Passivation Behavior of 2507 Super Duplex Stainless Steel in Hot Concentrated Seawater: Influence of Temperature and Seawater Concentration[J]. Acta Metallurgica Sinica (English Letters), 2022, 35(2): 326-340.

Figures/Tables 24

Table 1 Chemical composition of the 2507 super duplex stainless steel (wt%)

C	Si	N	Mo	Ni	Cr	P	S	Mn	Fe
0.03	0.8	0.27	3.43	6.74	25.15	0.035	0.02	1.2	Bal.

Fig. 1 Microstructure of 2507 SDSS observed by optical microscopy a SEM b. (α: ferrite, γ: austenite)

Table 2 Elemental composition (wt%) of the two phase of 2507 SDSS

Phase	C	Mo	Cr	Ni
Ferrite	1.76	5.23	27.48	4.97
Austenite	1.45	2.91	25.46	7.27

Table 3 Chemical composition of the concentrated artificial seawater (g/L)

Concentration	NaCl	Na₂SO₄	NaHCO₃	KCl	MgCl₂·6H₂O	CaCl₂	KBr
1 time	24.53	4.09	0.201	0.695	11.1	1.16	0.101
2 times	49.06	8.18	0.402	1.390	22.2	2.32	0.202
3 times	73.59	12.27	0.603	2.085	33.3	3.48	0.303

Fig. 2 Open circuit potential of 2507 SDSS in the artificial seawater with different concentration multiples a 1 time, b 2 times, c 3 times, the calculated terminal OCP at the end of the test d

Fig. 3 Polarization curves of 2507 SDSS in the artificial seawater with different concentration multiples: a 1 time, b 2 times, c 3 times

Table 4 Corrosion potential and breakdown/oxygen evaluation potential of 2507 SDSS in the artificial seawater with different concentrations and temperatures

Temperature (℃)	Corrosion potential, E_corr (V_SCE)			Oxygen evolution potential (V_SCE)			Breaking potential (V_SCE)
Temperature (℃)	1 time	2 times	3 times	1 time	2 times	3 times	1 time	2 times	3 times
25	- 0.390	- 0.313	- 0.304	0.995	1.018	0.922
50	- 0.311	- 0.320	- 0.321	0.910	0.904	0.853
75	- 0.401	- 0.389	- 0.361				0.641	0.498	0.768
90	- 0.502	- 0.401	- 0.407				0.273	0.360	0.262

Fig. 4 Potentiostatic current density of 2507 SDSS in the original artificial seawater with different temperatures a and in the 75 °C seawater with different concentrations b

Fig. 5 EIS of 2507 SDSS in the original artificial seawater with different temperatures a and in the 75 °C seawater with different concentrations b

Table 5 Fitted EIS parameters of 2507 super duplex stainless steel in the original artificial seawater with different temperatures

T (℃)	R_s (Ω cm²)	Q₁ 10^-6(Ω^-1 cm^-2 sⁿ)	n	R₁ (μF cm²)	C_eff (nm)	d
25	8.8	40.9	0.88	742.2	14.07	1.96
50	6.0	62.4	0.84	713.6	14.38	1.92
75	4.5	85.3	0.82	310.9	15.09	1.83
90	4.1	91.7	0.81	61.48	13.85	1.99

Table 6 Fitted EIS parameters of 2507 super duplex stainless steel in the 75 ℃ seawater with different concentrations

Concentration	R_s (Ω cm²)	Q₁ 10^-6(Ω^-1 cm^-2 sⁿ)	n	R₁ (kΩ cm²)	C_eff (μF cm²)	d (nm)
1 time	4.5	85.3	0.82	310.9	15.09	1.83
2 times	3.2	133.2	0.77	281.2	13.06	2.11
3 times	2.9	150.7	0.76	50.0	12.79	2.16

Fig. 6 Variation of Q1 and R1 of 2507 SDSS in the original artificial seawater with different temperatures a and in the 75 °C seawater with different concentrations b

Fig. 7 Variation of film thickness of 2507 SDSS in artificial seawater with different temperatures and concentrations

Fig. 8 Mott-Schottky plots of the passive film on 2507 SDSS in artificial seawater with 1 time a, 2 times b, 3 times c of concentration at different temperatures as well as the calculated donor densities d

Table 7 Calculated donor density and flat band potential of the passive film formed in the artificial seawater with different temperatures and concentrations

Temperature (℃)	Donor density (× 10²⁰ cm^-3)			Flat band potential (V_SCE)
Temperature (℃)	1 time	2 times	3 times	1 time	2 times	3 times
25	5.59	6.32	7.28	- 0.38	- 0.38	- 0.35
50	6.18	6.39	6.68	- 0.39	- 0.37	- 0.36
75	6.32	6.69	7.75	- 0.39	- 0.35	- 0.33
90	7.48	7.96	9.36	- 0.39	- 0.38	- 0.32

Fig. 9 Dependence of the anodic current density on the polarization time in the seawater with different concentrations a the calculated critical pitting temperature b

Fig. 10 XPS cationic fraction in the passive film of 2507 SDSS in the double enriched artificial seawater at different temperatures

Fig. 11 Detailed XPS spectra of Fe 2p3/2 of the passive film formed on 2507 SDSS in the double enriched artificial seawater at 25 °C a, 50 °C b, 75 °C c, 90 °C d

Table 8 Parameters used for deconvolution of XPS spectra for the main species present in the passive film and atomic percent of the film composition at different temperatures

Components	25 ℃		50 ℃		75 ℃		90 ℃
Components	Binding energy (eV)	Content (%)	Binding energy (eV)	Content (%)	Binding energy (eV)	Content (%)	Binding energy (eV)	Content (%)
O^2-	530.0	21.1	530.0	32.1	530.0	18.2	529.9	32.1
OH^-	531.3	74.2	531.3	61.5	531.1	77.6	531.2	62.3
H₂O	532.7	4.7	532.7	6.4	532.7	4.2	532.7	5.6
Fe⁰	706.6	12.3	706.6	7.2	706.5	7.6	706.5	38.6
FeO	708.8	15.6	708.8	16.8	708.8	12.9	708.8	25.9
Fe₂O₃	710.2	40.8	710.2	27.7	710.3	48.3	710.1	14.2
FeOOH	711.2	5.8	711.1	31.8	711.2	17.9	711.1	13.5
Fe(OH)₃	712.6	25.6	712.6	16.5	712.7	13.3	712.6	7.8
Fe(II)/Fe(III)	0.22		0.22		0.16		0.73
Cr⁰	573.7	10.9	573.7	10.9	573.7	9.6	573.7	10.4
Cr₂O₃	576.0	43.3	576.1	40.5	576.0	46.1	576.0	51.7
Cr(OH₎₃	577.3	45.7	577.2	48.6	577.2	44.5	577.2	37.8
Cr^ox/Fe^ox	0.53		0.63		0.62		2.99
Mo3d_5/2	227.6	11.4	227.6	12.8	227.6	14.6	227.6	20.7
Mo⁴⁺3d_5/2	229.3	11.1	229.3	12.8	229.3	9.1	229.3	10.5
Mo3d_3/2	230.7	7.7	230.7	8.6	230.7	9.8	230.7	13.9
Mo⁶⁺3d_5/2	232.2	35.2	232.1	34.3	232.1	36.1	232.1	28.7
Mo⁴⁺3d_3/2	233.5	11.1	233.5	8.6	233.5	6.1	233.4	7.0
Mo⁶⁺3d_3/2	235.1	23.6	235.1	22.9	235.1	24.2	235.1	19.2

Fig. 12 Detailed XPS spectra of Cr 2p3/2 of the passive film formed on 2507 SDSS in the double enriched artificial seawater at 25 °C a, 50 °C b, 75 °C c, 90 °C d

Fig. 13 Detailed XPS spectra of Mo 3d of the passive film film formed on 2507 SDSS in the double enriched artificial seawater at 25 °C a, 50 °C b, 75 °C c, 90 °C d

Fig. 14 Detailed XPS spectra of O 1 s of the passive film formed on 2507 SDSS in the double enriched artificial seawater at 25 °C a, 50 °C b, 75 °C c, 90 °C d

Fig. 15 Fractions of the metallic oxide/hydroxide species in the passive film on 2507 SDSS after immersion in the double enriched artificial seawater for 24 h

Fig. 16 Fractions of the oxygen-containing species in the passive film on 2507 SDSS after immersion in the double enriched artificial seawater for 24 h

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