J. Mater. Sci. Technol. ›› 2021, Vol. 64: 176-186.DOI: 10.1016/j.jmst.2020.05.070
• Research Article • Previous Articles Next Articles
Yuqiao Donga, Jiaqi Lib, Dake Xub,*(
), Guangling Songa,*(), Dan Liuc, Haipeng Wanga, M.Saleem Khand, Ke Yange, Fuhui Wangb
Received:2019-12-25
Accepted:2020-05-27
Published:2021-02-20
Online:2021-03-15
Contact:
Dake Xu,Guangling Song
About author:*. E-mail addresses: xudake@mail.neu.edu.cn (D. Xu)Yuqiao Dong, Jiaqi Li, Dake Xu, Guangling Song, Dan Liu, Haipeng Wang, M.Saleem Khan, Ke Yang, Fuhui Wang. Investigation of microbial corrosion inhibition of Cu-bearing 316L stainless steel in the presence of acid producing bacterium Acidithiobacillus caldus SM-1[J]. J. Mater. Sci. Technol., 2021, 64: 176-186.
| Element | C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Fe |
|---|---|---|---|---|---|---|---|---|---|---|
| 316L SS | 0.022 | 0.43 | 1.18 | 0.032 | 0.0006 | 16.78 | 10.5 | 2.09 | --- | Bal. |
| 316L-Cu SS | 0.004 | 0.56 | 0.03 | 0.008 | 0.004 | 17.77 | 14.6 | 3.11 | 3.35 | Bal. |
Table 1 Chemical composition of 316L SS and 316L-Cu SS.
| Element | C | Si | Mn | P | S | Cr | Ni | Mo | Cu | Fe |
|---|---|---|---|---|---|---|---|---|---|---|
| 316L SS | 0.022 | 0.43 | 1.18 | 0.032 | 0.0006 | 16.78 | 10.5 | 2.09 | --- | Bal. |
| 316L-Cu SS | 0.004 | 0.56 | 0.03 | 0.008 | 0.004 | 17.77 | 14.6 | 3.11 | 3.35 | Bal. |
Fig. 1. Variations of EOCP and Rp vs. exposure time of 316L SS and 316L-Cu SS in abiotic and biotic media for 14 d.
Fig. 2. Bode and Nyquist plots of 316L SS in the abiotic medium (A, A’), biotic medium (B, B’) and 316L-Cu SS in the abiotic medium (C, C’), biotic medium (D, D’) after 1, 4, 7, 10 and 14 d.
Fig. 3. Physical models and the corresponding equivalent circuits used to fit the EIS data of 316L SS and 316L-Cu SS coupons.
| Duration (days) | Rs (Ω cm2) | Qdl×10-5 (Ω-1 sn cm-2) | ndl | Rct×103 (kΩ cm2) | Σχ2 (10-3) |
|---|---|---|---|---|---|
| 316L SS in the abiotic medium | |||||
| 1 | 62.5 ± 10.8 | 4.7 ± 1.0 | 0.95 ± 0.04 | 2.3 ± 0.4 | 0.5 ± 0.09 |
| 4 | 74.5 ± 12.5 | 3.6 ± 0.7 | 0.92 ± 0.01 | 2.7 ± 0.5 | 0.3 ± 0.04 |
| 7 | 72.1 ± 12.4 | 3.8 ± 0.8 | 0.92 ± 0.01 | 3.3 ± 0.7 | 0.3 ± 0.03 |
| 10 | 75.2 ± 14.2 | 3.7 ± 0.6 | 0.92 ± 0.01 | 3.9 ± 0.6 | 0.4 ± 0.08 |
| 14 | 73.9 ± 11.6 | 3.2 ± 0.6 | 0.92 ± 0.01 | 4.6 ± 0.8 | 0.6 ± 0.1 |
| 316L-Cu SS in the abiotic medium | |||||
| 1 | 45.2 ± 2.6 | 3.9 ± 0.3 | 0.92 ± 0.01 | 4.0 ± 0.6 | 0.5 ± 0.1 |
| 4 | 40.1 ± 4.2 | 3.4 ± 0.2 | 0.92 ± 0.01 | 6.8 ± 2.1 | 0.4 ± 0.2 |
| 7 | 36.8 ± 4.0 | 3.4 ± 0.2 | 0.92 ± 0.01 | 6.8 ± 1.8 | 0.5 ± 0.2 |
| 10 | 30.6 ± 1.2 | 3.8 ± 0.1 | 0.92 ± 0.01 | 7.1 ± 1.9 | 0.3 ± 0.02 |
| 14 | 29.9 ± 4.7 | 3.3 ± 0.7 | 0.92 ± 0.03 | 6.8 ± 1.4 | 0.5 ± 0.02 |
| 316L SS in the biotic medium | |||||
| 1 | 50.8 ± 2.1 | 3.9 ± 0.5 | 0.93 ± 0.01 | 1.6 ± 0.5 | 3.5 ± 2.9 |
| 4 | 48.4 ± 0.1 | 3.7 ± 0.9 | 0.94 ± 0.01 | 3.7 ± 1.3 | 0.5 ± 0.1 |
| 7 | 38.1 ± 0.05 | 5.1 ± 0.8 | 0.92 ± 0.01 | 3.0 ± 0.03 | 0.6 ± 0.06 |
| 10 | 27.0 ± 4.3 | 5.5 ± 1.9 | 0.89 ± 0.03 | 2.2 ± 0.8 | 0.8 ± 0.6 |
| 14 | 27.9 ± 7.5 | 6.7 ± 3.8 | 0.90 ± 0.01 | 1.9 ± 0.9 | 1.34 ± 0.3 |
| 316L-Cu SS in the biotic medium | |||||
| 1 | 43.4 ± 1.1 | 3.9 ± 0.6 | 0.98 ± 0.01 | 3.1 ± 0.3 | 0.4 ± 0.1 |
| 4 | 39.1 ± 0.4 | 3.2 ± 0.5 | 0.94 ± 0.01 | 5.8 ± 0.8 | 0.3 ± 0.07 |
| 7 | 33.4 ± 0.9 | 3.2 ± 0.5 | 0.95 ± 0.01 | 6.4 ± 0.1 | 0.5 ± 0.3 |
| 10 | 30.9 ± 0.4 | 3.4 ± 0.6 | 0.95 ± 0.01 | 4.9 ± 0.7 | 0.5 ± 0.3 |
| 14 | 27.6 ± 1.4 | 3.4 ± 0.6 | 0.95 ± 0.01 | 4.6 ± 1.8 | 0.9 ± 0.6 |
Table 2 EIS parameters of 316L SS and 316L-Cu SS in abiotic and biotic media.
| Duration (days) | Rs (Ω cm2) | Qdl×10-5 (Ω-1 sn cm-2) | ndl | Rct×103 (kΩ cm2) | Σχ2 (10-3) |
|---|---|---|---|---|---|
| 316L SS in the abiotic medium | |||||
| 1 | 62.5 ± 10.8 | 4.7 ± 1.0 | 0.95 ± 0.04 | 2.3 ± 0.4 | 0.5 ± 0.09 |
| 4 | 74.5 ± 12.5 | 3.6 ± 0.7 | 0.92 ± 0.01 | 2.7 ± 0.5 | 0.3 ± 0.04 |
| 7 | 72.1 ± 12.4 | 3.8 ± 0.8 | 0.92 ± 0.01 | 3.3 ± 0.7 | 0.3 ± 0.03 |
| 10 | 75.2 ± 14.2 | 3.7 ± 0.6 | 0.92 ± 0.01 | 3.9 ± 0.6 | 0.4 ± 0.08 |
| 14 | 73.9 ± 11.6 | 3.2 ± 0.6 | 0.92 ± 0.01 | 4.6 ± 0.8 | 0.6 ± 0.1 |
| 316L-Cu SS in the abiotic medium | |||||
| 1 | 45.2 ± 2.6 | 3.9 ± 0.3 | 0.92 ± 0.01 | 4.0 ± 0.6 | 0.5 ± 0.1 |
| 4 | 40.1 ± 4.2 | 3.4 ± 0.2 | 0.92 ± 0.01 | 6.8 ± 2.1 | 0.4 ± 0.2 |
| 7 | 36.8 ± 4.0 | 3.4 ± 0.2 | 0.92 ± 0.01 | 6.8 ± 1.8 | 0.5 ± 0.2 |
| 10 | 30.6 ± 1.2 | 3.8 ± 0.1 | 0.92 ± 0.01 | 7.1 ± 1.9 | 0.3 ± 0.02 |
| 14 | 29.9 ± 4.7 | 3.3 ± 0.7 | 0.92 ± 0.03 | 6.8 ± 1.4 | 0.5 ± 0.02 |
| 316L SS in the biotic medium | |||||
| 1 | 50.8 ± 2.1 | 3.9 ± 0.5 | 0.93 ± 0.01 | 1.6 ± 0.5 | 3.5 ± 2.9 |
| 4 | 48.4 ± 0.1 | 3.7 ± 0.9 | 0.94 ± 0.01 | 3.7 ± 1.3 | 0.5 ± 0.1 |
| 7 | 38.1 ± 0.05 | 5.1 ± 0.8 | 0.92 ± 0.01 | 3.0 ± 0.03 | 0.6 ± 0.06 |
| 10 | 27.0 ± 4.3 | 5.5 ± 1.9 | 0.89 ± 0.03 | 2.2 ± 0.8 | 0.8 ± 0.6 |
| 14 | 27.9 ± 7.5 | 6.7 ± 3.8 | 0.90 ± 0.01 | 1.9 ± 0.9 | 1.34 ± 0.3 |
| 316L-Cu SS in the biotic medium | |||||
| 1 | 43.4 ± 1.1 | 3.9 ± 0.6 | 0.98 ± 0.01 | 3.1 ± 0.3 | 0.4 ± 0.1 |
| 4 | 39.1 ± 0.4 | 3.2 ± 0.5 | 0.94 ± 0.01 | 5.8 ± 0.8 | 0.3 ± 0.07 |
| 7 | 33.4 ± 0.9 | 3.2 ± 0.5 | 0.95 ± 0.01 | 6.4 ± 0.1 | 0.5 ± 0.3 |
| 10 | 30.9 ± 0.4 | 3.4 ± 0.6 | 0.95 ± 0.01 | 4.9 ± 0.7 | 0.5 ± 0.3 |
| 14 | 27.6 ± 1.4 | 3.4 ± 0.6 | 0.95 ± 0.01 | 4.6 ± 1.8 | 0.9 ± 0.6 |
| Duration (days) | 1 | 4 | 7 | 14 |
|---|---|---|---|---|
| ηR (%) | 43.3 ± 5.1 | 30.2 ± 6 | 54.5 ± 0.4 | 54.3 ± 2.1 |
Table 3 Inhibition efficiency of 316L-Cu SS specimen against A. caldus SM-1.
| Duration (days) | 1 | 4 | 7 | 14 |
|---|---|---|---|---|
| ηR (%) | 43.3 ± 5.1 | 30.2 ± 6 | 54.5 ± 0.4 | 54.3 ± 2.1 |
Fig. 4. Polarization curves of 316L SS and 316L-Cu SS exposed to abiotic and biotic media after 14 d of incubation.
| Medium | icorr (μA cm-2) | Ecorr (V vs. SCE) | Epit (V vs. SCE) |
|---|---|---|---|
| 316L SS in the abiotic medium | 0.054 ± 0.004 | -0.20 ± 0.01 | 1.5 ± 0.01 |
| 316L-Cu SS in the abiotic medium | 0.046 ± 0.001 | -0.21 ± 0.007 | 1.4 ± 0.1 |
| 316L SS in the biotic medium | 1.6 ± 0.4 | -0.37 ± 0.05 | 1.0 ± 0.007 |
| 316L-Cu SS in the biotic medium | 0.035 ± 0.007 | -0.072 ± 0.09 | 1.2 ± 0.04 |
Table 4 The electrochemical corrosion parameters calculated by the polarization curves of 316L SS and 316L-Cu SS coupons after 14 d of incubation.
| Medium | icorr (μA cm-2) | Ecorr (V vs. SCE) | Epit (V vs. SCE) |
|---|---|---|---|
| 316L SS in the abiotic medium | 0.054 ± 0.004 | -0.20 ± 0.01 | 1.5 ± 0.01 |
| 316L-Cu SS in the abiotic medium | 0.046 ± 0.001 | -0.21 ± 0.007 | 1.4 ± 0.1 |
| 316L SS in the biotic medium | 1.6 ± 0.4 | -0.37 ± 0.05 | 1.0 ± 0.007 |
| 316L-Cu SS in the biotic medium | 0.035 ± 0.007 | -0.072 ± 0.09 | 1.2 ± 0.04 |
Fig. 5. SEM images of biofilm on the coupon surface of 316L SS (A) and 316L-Cu SS (B) after exposure to A. caldus SM-1 for 7 d.
Fig. 6. CLSM images of biofilm on the coupon surface of (A) 316L SS after 7 d, (A’) 316L-Cu SS after 7 d, (B) 316L SS after 14 d, and (B’) 316L-Cu SS after 14 d.
Fig. 7. Live and dead sessile cell counts on the coupon surfaces of 316L SS and 316L-Cu SS after 7 and 14 d.
Fig. 8. Images of the largest pit depth after 14 d on (A) 316L SS in the biotic medium, (A') 316L-Cu SS in the biotic medium, (B) 316L SS in the abiotic medium, (B') 316L-Cu SS in the abiotic medium.
Fig. 9. (A) The wide XPS spectrum of 316L SS and 316L-Cu SS coupons after 14-day incubation in abiotic and biotic media; high resolution XPS spectra of Cu 2p, Cr 2p, Fe 2p in the biotic medium, (B), (C) and (D) for 316L-Cu SS coupon, (C’) and (D’) for 316L SS coupon.
| Duration (days) | 316L SS | 316L-Cu SS |
|---|---|---|
| 0 | 3.20 ± 0.001 | 3.20 ± 0.001 |
| 1 | 3.19 ± 0.014 | 3.18 ± 0.014 |
| 4 | 2.72 ± 0.057 | 2.72 ± 0.007 |
| 7 | 2.24 ± 0.064 | 2.34 ± 0.021 |
| 10 | 2.06 ± 0.057 | 2.18 ± 0.001 |
| 14 | 1.77 ± 0.049 | 1.87 ± 0.049 |
Table 5 pH variation of 316L SS and 316L-Cu SS coupons exposed to the biotic medium.
| Duration (days) | 316L SS | 316L-Cu SS |
|---|---|---|
| 0 | 3.20 ± 0.001 | 3.20 ± 0.001 |
| 1 | 3.19 ± 0.014 | 3.18 ± 0.014 |
| 4 | 2.72 ± 0.057 | 2.72 ± 0.007 |
| 7 | 2.24 ± 0.064 | 2.34 ± 0.021 |
| 10 | 2.06 ± 0.057 | 2.18 ± 0.001 |
| 14 | 1.77 ± 0.049 | 1.87 ± 0.049 |
| Duration (days) | Maximum Cu2+ release (mg L-1) | Average Cu2+ release (mg L-1) |
|---|---|---|
| 14 | 0.46 | 0.39 ± 0.07 |
Table 6 The release of Cu2+ from 316L-Cu SS in the medium after 14 d.
| Duration (days) | Maximum Cu2+ release (mg L-1) | Average Cu2+ release (mg L-1) |
|---|---|---|
| 14 | 0.46 | 0.39 ± 0.07 |
Fig. 10. Schematic illustration of antibacterial and anticorrosion mechanism for 316L-Cu SS.
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