Effect of pH on the Electrochemical Behaviour and Passive Film Composition of 316L Stainless Steel

doi:10.1007/s40195-018-0794-5

摘要/Abstract

Abstract:

The effect of pH on the electrochemical behaviour and passive film composition of 316L stainless steel in alkaline solutions was studied using electrochemical measurements and a surface analysis method. The critical pH of 12.5 was found for the conversion from pitting corrosion to the oxygen evolution reaction (OER). OER was kinetically faster than pitting corrosion when both reactions could occur, and OER could postpone pitting corrosion. This resulted in pitting being initiated during the reversing scan in the cyclic polarization at the critical pH. According to the X-ray photoelectron spectroscopy analysis, the content of Cr and Mo decreased with pH, while Fe content increased. This induced the degradation of the passive film, which resulted in the higher passive current densities under more alkaline conditions. The selective dissolution of Mo at high pH was found, which demonstrated that the addition of Mo in austenitic stainless steels might not be beneficial to the corrosion resistance of 316L in strong alkaline solutions.

Key words: Stainless steel, pH, Polarization, XPS, Passive films

. [J]. Acta Metallurgica Sinica (English Letters), 2019, 32(5): 585-598.

Zhu Wang, Zi-Qiang Zhou, Lei Zhang, Jia-Yuan Hu, Zi-Ru Zhang, Min-Xu Lu. Effect of pH on the Electrochemical Behaviour and Passive Film Composition of 316L Stainless Steel[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(5): 585-598.

图/表 20

Table 1 Chemical composition of 316L austenitic stainless steel (wt%)

C	Si	Mn	P	S	Cr	Mo	Ni	Fe
0.022	0.47	1.2	0.02	0.003	16.7	2.35	10	Bal.

Fig. 1 Cyclic polarization curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 12, e pH 13, f pH 13.5

Fig. 2 SEM images of the 316L samples after the cyclic polarization tests conducted under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 13, e pH 13.5

Fig. 3 Cyclic polarization curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature at pH 12.5

Fig. 4 Surface morphologies of the work electrode obtained during the cyclic polarization Test 2 at: a potential point 1, b potential point 2

Fig. 5 Passive current densities extracted from the polarization curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions

Fig. 6 j-t curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions

Fig. 7 Nyquist plots obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions

Fig. 8 Equivalent circuits used for the EIS analysis

Table 2 Calculated equivalent circuit parameters

pH	R_s (Ω)	Error (%)	Q _f				R_f (kΩ)	Error (%)
pH	R_s (Ω)	Error (%)	Y_o (Ω^-1 cm^-2 sⁿ)	Error (%)	n	Error (%)	R_f (kΩ)	Error (%)
7	11.91	0.4	4.59 × 10^-5	3.5	0.9	1.3	320.6	9.8
9	9.1	1.3	5.08 × 10^-5	2.6	0.89	3.2	171.6	9.2
11	8.15	2.2	5.74 × 10^-5	4.3	0.87	4.3	119.6	9.7
13	5.17	1.6	5.32 × 10^-5	3.7	0.91	2.9	79.11	8.9

Fig. 9 High-resolution XPS spectra of Cr 2p3/2 obtained on 316L stainless steel after the potentiostatic tests measured in NaCl solutions at ambient temperature under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 13

Fig. 10 High-resolution XPS spectra of Fe 2p3/2 obtained on 316L stainless steel after the potentiostatic tests measured in NaCl solutions at ambient temperature under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 13

Fig. 11 High-resolution XPS spectra of Mo 3d obtained on 316L stainless steel after the potentiostatic tests measured in NaCl solutions at ambient temperature under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 13

Fig. 12 High-resolution XPS spectra of O 1s obtained on 316L stainless steel after the potentiostatic tests measured in NaCl solutions at ambient temperature under various pH conditions: a pH 7, b pH 9, c pH 11, d pH 13

Fig. 13 Characteristic potentials extracted from the polarization curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions

Fig. 14 E-t curves obtained for 316L stainless steel measured in NaCl solutions at ambient temperature under various pH conditions

Fig. 15 Schematic diagrams of the potential variation during galvanostatic tests: a used for illustrating the galvanostatic plots measured at pH 7, 9 and 11; b used for illustrating the galvanostatic plot measured at pH 13

Fig. 16 Schematic diagrams for illustrating the cyclic polarization plots measured at pH 12.5

Fig. 17 Atomic concentrations of Fe, Cr, Mo, and Ni in the passive film as a function of pH

Fig. 18 Enrichment factors of Fe, Cr, Mo, and Ni as a function of pH

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