J. Mater. Sci. Technol. ›› 2018, Vol. 34 ›› Issue (8): 1349-1358.DOI: 10.1016/j.jmst.2017.11.004
Special Issue: Corrosion in 2018
• Orginal Article • Previous Articles Next Articles
Fang Xueab, Xin Weia, Junhua Donga(), Ini-Ibehe Nabuk Etima, Changgang Wanga, Wei Kea
Received:
2017-07-28
Revised:
2017-09-22
Accepted:
2017-10-31
Online:
2018-08-17
Published:
2018-08-22
Fang Xue, Xin Wei, Junhua Dong, Ini-Ibehe Nabuk Etim, Changgang Wang, Wei Ke. Effect of residual dissolved oxygen on the corrosion behavior of low carbon steel in 0.1 M NaHCO3 solution[J]. J. Mater. Sci. Technol., 2018, 34(8): 1349-1358.
Fig. 2. XRD results of corrosion products on low carbon steel in 0.1 M NaHCO3 solution with different oxygen concentrations: DO = 2.1 ppb, 310 ppb, 8 ppm.
Fig. 3. Micro-morphologies of surface and cross section of low carbon steel after immersed in 0.1 M NaHCO3 solutions with different dissolved oxygen concentrations for 20 days: DO = 2.1 ppb (a, a'); DO = 310 ppb (b, b'); DO = 8 ppm (c, c').
Fig. 4. Open circuit potential (V vs. SCE) vs. time (day) in 0.1 M NaHCO3 solution with different dissolved oxygen concentrations: 2.1 ppb, 310 ppb, and 8 ppm.
No. | Electrode reaction | Equilibrium potential equation (vs. SCE) | E (V) vs. SCE |
---|---|---|---|
2 | 2H+ + 2e → H2 | E = -0.2438-0.05916pH-0.02958lgPH2 | -0.7366 |
3 | Fe + 2H2O → Fe(OH)2 + 2H+ + 2e | E = -0.3044-0.05916 pH | -0.7972 |
4 | 2Fe + 2H2O + HCO3- → Fe2(OH)2CO3 + 3H+ + 4e | E = -0.522-0.04433pH-0.01479lg[HCO3-] | -0.8765 |
5 | 6Fe + 12H2O + HCO3- → Fe6(OH)12CO3 + 13H+ + 14e | E = -0.4021-0.05488pH-0.004221lg[HCO3-] | -0.8550 |
6 | 3Fe + 4H2O → Fe3O4 + 8H+ + 8e | E = -0.3301-0.05916 pH | -0.8229 |
7 | Fe + 2H2O → α-FeOOH + 3H+ + 3e | E = -0.2609-0.05916 pH | -0.7537 |
8 | Fe(OH)2 → α-FeOOH + H+ + e | E = -0.2314-0.05916 pH | -0.7242 |
9 | Fe2(OH)2CO3 + 2H2O → 2α-FeOOH + HCO3- + 3H+ + 2e | E = 0.2028-0.08865pH + 0.02958lg[HCO3-] | -0.5652 |
10 | Fe6(OH)12CO3 → 6α-FeOOH + HCO3- + 5H+ + 4e | E = 0.1387-0.07388pH-0.01479lg[HCO3-] | -0.4915 |
11 | Fe3O4 + 2H2O → 3α-FeOOH + H+ + e | E = 0.1060-0.05916 pH | -0.3868 |
12 | 8α-FeOOH + Fe3+ + 3e → 3Fe3O4 + 4H2O | E=0.0699 + 0.01972lg[Fe3+] | -0.0287 |
13 | 5α-FeOOH + Fe3+ + HCO3- + 2H2O + 2H+ + 4e → Fe6(OH)12CO3 | E=0.1522-0.02958pH + 0.01478lg[HCO3-] + 0.01478lg[Fe3+] | -0.1799 |
14 | 5α-FeOOH + Fe2+ + HCO3- + 2H2O + 2H+ + 3e → Fe6(OH)12CO3 | E=0.0318-0.03944 pH +0.01972lg[HCO3-] + 0.01972lg[Fe2+] | -0.4151 |
Table 1 Possible electrode reactions of low carbon steel in 0.1 M NaHCO3 solution of pH 8.33.
No. | Electrode reaction | Equilibrium potential equation (vs. SCE) | E (V) vs. SCE |
---|---|---|---|
2 | 2H+ + 2e → H2 | E = -0.2438-0.05916pH-0.02958lgPH2 | -0.7366 |
3 | Fe + 2H2O → Fe(OH)2 + 2H+ + 2e | E = -0.3044-0.05916 pH | -0.7972 |
4 | 2Fe + 2H2O + HCO3- → Fe2(OH)2CO3 + 3H+ + 4e | E = -0.522-0.04433pH-0.01479lg[HCO3-] | -0.8765 |
5 | 6Fe + 12H2O + HCO3- → Fe6(OH)12CO3 + 13H+ + 14e | E = -0.4021-0.05488pH-0.004221lg[HCO3-] | -0.8550 |
6 | 3Fe + 4H2O → Fe3O4 + 8H+ + 8e | E = -0.3301-0.05916 pH | -0.8229 |
7 | Fe + 2H2O → α-FeOOH + 3H+ + 3e | E = -0.2609-0.05916 pH | -0.7537 |
8 | Fe(OH)2 → α-FeOOH + H+ + e | E = -0.2314-0.05916 pH | -0.7242 |
9 | Fe2(OH)2CO3 + 2H2O → 2α-FeOOH + HCO3- + 3H+ + 2e | E = 0.2028-0.08865pH + 0.02958lg[HCO3-] | -0.5652 |
10 | Fe6(OH)12CO3 → 6α-FeOOH + HCO3- + 5H+ + 4e | E = 0.1387-0.07388pH-0.01479lg[HCO3-] | -0.4915 |
11 | Fe3O4 + 2H2O → 3α-FeOOH + H+ + e | E = 0.1060-0.05916 pH | -0.3868 |
12 | 8α-FeOOH + Fe3+ + 3e → 3Fe3O4 + 4H2O | E=0.0699 + 0.01972lg[Fe3+] | -0.0287 |
13 | 5α-FeOOH + Fe3+ + HCO3- + 2H2O + 2H+ + 4e → Fe6(OH)12CO3 | E=0.1522-0.02958pH + 0.01478lg[HCO3-] + 0.01478lg[Fe3+] | -0.1799 |
14 | 5α-FeOOH + Fe2+ + HCO3- + 2H2O + 2H+ + 3e → Fe6(OH)12CO3 | E=0.0318-0.03944 pH +0.01972lg[HCO3-] + 0.01972lg[Fe2+] | -0.4151 |
Fig. 8. Electrochemical impedance spectroscopy of low carbon steel in 0.1 M NaHCO3 solution with DO = 2.1 ppb: |Z|-Frequency plot (a), Phase Angle-Frequency plot (a') and Nyquist plot (a”), respectively.
Fig. 9. Electrochemical impedance spectroscopy of low carbon steel in 0.1 M NaHCO3 solution with DO = 310 ppb: |Z|-Frequency plot (b), Phase Angle-Frequency plot (b') and Nyquist plot (b”), respectively.
Fig. 10. Electrochemical impedance spectroscopy of low carbon steel in 0.1 M NaHCO3 solution with DO = 8 ppm: |Z|-Frequency plot (c), Phase Angle-Frequency plot (c') and Nyquist plot (c”), respective.
Fig. 11. Equivalent circuit for fitting the EIS data of low carbon steel in 0.1 M NaHCO3 solution with dissolved oxygen of 2.1 ppb (Rs - solution resistance, Qdl - CPE of double electrical layer, Rct - charge transfer resistance, Qgr - CPE of goethite reduction, Rgr - resistance of goethite reduction, Qo - CPE of oxidization from green rust to goethite, Ro- resistance of oxidization from green rust to goethite).
Fig. 12. Equivalent circuit for fitting the EIS data of low carbon steel in 0.1 M NaHCO3 solution with dissolved oxygen of 310 ppb (Rs - solution resistance, Qdl/Cdl - CPE/capacitance of double electrical layer, Rct - charge transfer resistance, Qor - CPE of oxygen reduction, Ror- resistance of oxygen reduction, W- Warburg impedance, Qo - CPE of oxidization from green rust to goethite, Ro- resistance of oxidization from green rust to goethite).
Fig. 13. Equivalent circuit for fitting the EIS data of low carbon steel in 0.1 M NaHCO3 solution with dissolved oxygen of 8 ppm (Rs - solution resistance, Qdl/Cdl - CPE/capacitance of double electrical layer, Rct - charge transfer resistance, Qgr - CPE of goethite reduction, Rgr - resistance of goethite reduction, Qor - CPE of oxygen reduction, Ror- resistance of oxygen reduction, W- Warburg impedance).
Time (day) | Rs (Ω cm2) | Ygr (mS sn cm-2) | ngr- | Rgr (Ω cm2) | Yo (mS sn cm-2) | no - | Ro (Ω cm2) | Ydl (mS sn cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|
1 | 29.44 | 0.1718 | 0.8619 | 3.036 | ||||||
4 | 26.39 | 0.4096 | 0.702 | 1147 | 0.6563 | 0.7557 | 8.095 | |||
7 | 22.25 | 4.972 | 0.3721 | 1375 | 1.734 | 0.6722 | 11.19 | |||
10 | 6.127 | 1.719 | 0.5692 | 5167 | 4.275 | 0.8383 | 2.444 | 0.07114 | 0.3269 | 10.67 |
13 | 6.036 | 8.992 | 0.4016 | 1231 | 1.394 | 0.6775 | 2.255 | 0.2514 | 0.5102 | 9.218 |
16 | 4.219 | 20.11 | 0.3357 | 2991 | 1.31 | 0.6512 | 3.609 | 0.39 | 0.8523 | 16.37 |
22 | 8.275 | 1.589 | 0.5911 | 2658 | 4.627 | 0.978 | 2.785 | 2.101 | 0.9999 | 15.11 |
Table 2 Fitting results of the measured EIS data in 0.1 M NaHCO3 solution with dissolved oxygen concentration of 2.1 ppb.
Time (day) | Rs (Ω cm2) | Ygr (mS sn cm-2) | ngr- | Rgr (Ω cm2) | Yo (mS sn cm-2) | no - | Ro (Ω cm2) | Ydl (mS sn cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|
1 | 29.44 | 0.1718 | 0.8619 | 3.036 | ||||||
4 | 26.39 | 0.4096 | 0.702 | 1147 | 0.6563 | 0.7557 | 8.095 | |||
7 | 22.25 | 4.972 | 0.3721 | 1375 | 1.734 | 0.6722 | 11.19 | |||
10 | 6.127 | 1.719 | 0.5692 | 5167 | 4.275 | 0.8383 | 2.444 | 0.07114 | 0.3269 | 10.67 |
13 | 6.036 | 8.992 | 0.4016 | 1231 | 1.394 | 0.6775 | 2.255 | 0.2514 | 0.5102 | 9.218 |
16 | 4.219 | 20.11 | 0.3357 | 2991 | 1.31 | 0.6512 | 3.609 | 0.39 | 0.8523 | 16.37 |
22 | 8.275 | 1.589 | 0.5911 | 2658 | 4.627 | 0.978 | 2.785 | 2.101 | 0.9999 | 15.11 |
Time (day) | Rs (Ω cm2) | Yor (mS sn cm-2) | nor - | Ror (Ω cm2) | Yw (mS s0.5 cm-2) | Yo (mS sn cm-2) | no - | Ro (Ω cm2) | Ydl/Cdl (mS sn cm-2/mF cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 38.46 | 12.8 | 0.5109 | 465.5 | 0.153 | 0.591 | 0.7519 | 3.041 | |||
2 | 27.16 | 0.1045 | 0.8899 | 1503 | 0.003872 | 1.404 | 0.7369 | 3.786 | |||
5 | 23.94 | 0.00867 | 1 | 2366 | 0.02473 | 0.5598 | 0.692 | 1.047 | |||
8 | 25.7 | 0.177 | 0.9327 | 2581 | 0.05467 | 1.059 | 0.6413 | 3.028 | |||
14 | 19.48 | 0.0957 | 0.8691 | 2571 | 0.02498 | 0.7507 | 0.9003 | 6.901 | 0.03879 | - | 2.108 |
20 | 19.56 | 0.1048 | 0.8823 | 2439 | 0.02972 | 0.1846 | 0.9279 | 7.843 | 0.02152 | - | 2.68 |
Table 3 Fitting results of measured EIS data in 0.1 M NaHCO3 solution with dissolved oxygen concentration of 310 ppb.
Time (day) | Rs (Ω cm2) | Yor (mS sn cm-2) | nor - | Ror (Ω cm2) | Yw (mS s0.5 cm-2) | Yo (mS sn cm-2) | no - | Ro (Ω cm2) | Ydl/Cdl (mS sn cm-2/mF cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 38.46 | 12.8 | 0.5109 | 465.5 | 0.153 | 0.591 | 0.7519 | 3.041 | |||
2 | 27.16 | 0.1045 | 0.8899 | 1503 | 0.003872 | 1.404 | 0.7369 | 3.786 | |||
5 | 23.94 | 0.00867 | 1 | 2366 | 0.02473 | 0.5598 | 0.692 | 1.047 | |||
8 | 25.7 | 0.177 | 0.9327 | 2581 | 0.05467 | 1.059 | 0.6413 | 3.028 | |||
14 | 19.48 | 0.0957 | 0.8691 | 2571 | 0.02498 | 0.7507 | 0.9003 | 6.901 | 0.03879 | - | 2.108 |
20 | 19.56 | 0.1048 | 0.8823 | 2439 | 0.02972 | 0.1846 | 0.9279 | 7.843 | 0.02152 | - | 2.68 |
Time (day) | Rs(Ω cm2) | Yor (mS sn cm-2) | nor - | Ror (Ω cm2) | Yw (mS s0.5 cm-2) | Ygr (mS sn cm-2) | ngr - | Rgr (Ω cm2) | Ydl/Cdl (mS sn cm-2/mF cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 35.6 | 5.258 | 0.9918 | 28190 | 5.854 | 0.179 | 0.8223 | 2.182 | |||
2 | 26.8 | 0.02261 | 0.4361 | 11520 | 0.01421 | 0.05268 | 0.9121 | 7.975 | 0.3131 | - | 0.755 |
5 | 31.02 | 0.04243 | 0.606 | 10590 | 0.01807 | 0.05182 | 0.9069 | 7.599 | 0.4423 | - | 1.568 |
8 | 30.61 | 0.05509 | 0.6968 | 45430 | 0.00651 | 0.05463 | 0.8996 | 19.18 | 0.2601 | - | 1.354 |
14 | 20.94 | 0.06286 | 0.717 | 46130 | 0.00558 | 0.06459 | 0.8648 | 2.834 | 0.1636 | - | 2.073 |
20 | 27.63 | 0.2105 | 0.7203 | 3319 | 0.01977 | 0.08822 | 0.8695 | 12.77 | 1.166 | - | 1.489 |
Table 4 Fitting results of measured EIS data in 0.1 M NaHCO3 solution with dissolved oxygen concentration of 8 ppm.
Time (day) | Rs(Ω cm2) | Yor (mS sn cm-2) | nor - | Ror (Ω cm2) | Yw (mS s0.5 cm-2) | Ygr (mS sn cm-2) | ngr - | Rgr (Ω cm2) | Ydl/Cdl (mS sn cm-2/mF cm-2) | ndl - | Rct (kΩ cm2) |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | 35.6 | 5.258 | 0.9918 | 28190 | 5.854 | 0.179 | 0.8223 | 2.182 | |||
2 | 26.8 | 0.02261 | 0.4361 | 11520 | 0.01421 | 0.05268 | 0.9121 | 7.975 | 0.3131 | - | 0.755 |
5 | 31.02 | 0.04243 | 0.606 | 10590 | 0.01807 | 0.05182 | 0.9069 | 7.599 | 0.4423 | - | 1.568 |
8 | 30.61 | 0.05509 | 0.6968 | 45430 | 0.00651 | 0.05463 | 0.8996 | 19.18 | 0.2601 | - | 1.354 |
14 | 20.94 | 0.06286 | 0.717 | 46130 | 0.00558 | 0.06459 | 0.8648 | 2.834 | 0.1636 | - | 2.073 |
20 | 27.63 | 0.2105 | 0.7203 | 3319 | 0.01977 | 0.08822 | 0.8695 | 12.77 | 1.166 | - | 1.489 |
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