Acta Metallurgica Sinica (English Letters) ›› 2017, Vol. 30 ›› Issue (4): 376-389.DOI: 10.1007/s40195-017-0532-4
Special Issue: 2017腐蚀虚拟专辑
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Robert Blair1, Batric Pesic1(), Jacob Kline1, Ian Ehrsam1, Krishnan Raja1
Received:
2017-02-20
Revised:
2017-02-20
Online:
2017-02-20
Published:
2017-05-17
Robert Blair, Batric Pesic, Jacob Kline, Ian Ehrsam, Krishnan Raja. Threshold Chloride Concentrations and Passivity Breakdown of Rebar Steel in Real Concrete Solution at Different pH Conditions with the Addition of Glycerol[J]. Acta Metallurgica Sinica (English Letters), 2017, 30(4): 376-389.
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Fig. 3 Cyclic polarizations of rebar in pH 12.5 solutions: a chloride additions (0, 50, and 65 × 10-3 mol/L), b chloride additions (65, 81, and 97 × 10-3 mol/L) and glycerol (2 wt%). Scan rate: 0.1667 mV/s
Fig. 4 Cyclic polarization of rebar in pH 12.5 solutions: a chloride additions (75, 80, 90, and 100 × 10-3 mol/L), b chloride additions (107, 120, and 135 × 10-3 mol/L) and glycerol (2 wt%). Scan rate: 1 mV/s
Fig. 5 Cyclic polarizations of rebar in pH 9 solutions with a chloride additions (0, 0.1, 0.2, and 0.3 × 10-3 mol/L), b chloride additions (0.2, 0.3, and 0.35 × 10-3 mol/L) and glycerol (2 wt%)
Fig. 6 Passivation behavior of rebar steel in pH 12.5 solution with no chloride addition characterized by electrochemical techniques: a potentiostatic plots, b Nyquist plots, c equivalent electrical circuit used to model EIS data, d Mott-Schottky plots
pH 12.5 | Polarization (VAg/AgCl) | Rsoln (ohm) | Rp (ohm) | Rf (ohm) | Qp (S sn) | n | Qf (S sm) | m |
---|---|---|---|---|---|---|---|---|
Control | +0.025 | 51.66 | 4.36 × 106 | 1.98 × 104 | 2.15 × 10-5 | 0.43 | 1.66 × 10-5 | 0.94 |
+0.6 | 80.7 | 4.13 × 104 | 4.31 × 101 | 3.08 × 10-5 | 0.88 | 2.65 × 10-5 | 0.89 | |
+0.65 | 71.14 | 1.53 × 103 | 1.45 × 101 | 9.51 × 10-5 | 0.90 | 3.16 × 10-5 | 0.91 | |
+0.025 | 50.41 | 3.31 × 105 | 9.65 × 104 | 3.21 × 10-5 | 0.62 | 1.88 × 10-5 | 0.95 | |
100 mM Cl- | +0.4 | 89.35 | 4.15 × 104 | 4.88 × 101 | 3.67 × 10-5 | 0.89 | 2.61 × 10-4 | 0.90 |
+0.45 | 94.55 | 3.09 × 103 | 2.17 × 101 | 6.63 × 10-5 | 0.91 | 3.39 × 10-5 | 0.93 | |
+0.025 | 55.43 | 1.79 × 106 | 1.14 × 104 | 8.06 × 10-6 | 0.28 | 1.61 × 10-5 | 0.94 | |
100 mM Cl- | +0.4 | 52.1 | 4.09 × 104 | 2.09 × 104 | 1.39 × 10-5 | 0.33 | 1.12 × 10-5 | 0.95 |
2 wt% GL | +0.45 | 53.63 | 7.70 × 103 | 2.15 × 104 | 2.63 × 10-4 | 0.32 | 1.30 × 10-5 | 0.93 |
+0.5 | 50.37 | 1.33 × 104 | 1.57 × 103 | 6.91 × 10-3 | 1.00 | 1.93 × 10-5 | 0.88 |
Table 1 Equivalent electrical circuit analysis of EIS data from experiments at pH 12.5
pH 12.5 | Polarization (VAg/AgCl) | Rsoln (ohm) | Rp (ohm) | Rf (ohm) | Qp (S sn) | n | Qf (S sm) | m |
---|---|---|---|---|---|---|---|---|
Control | +0.025 | 51.66 | 4.36 × 106 | 1.98 × 104 | 2.15 × 10-5 | 0.43 | 1.66 × 10-5 | 0.94 |
+0.6 | 80.7 | 4.13 × 104 | 4.31 × 101 | 3.08 × 10-5 | 0.88 | 2.65 × 10-5 | 0.89 | |
+0.65 | 71.14 | 1.53 × 103 | 1.45 × 101 | 9.51 × 10-5 | 0.90 | 3.16 × 10-5 | 0.91 | |
+0.025 | 50.41 | 3.31 × 105 | 9.65 × 104 | 3.21 × 10-5 | 0.62 | 1.88 × 10-5 | 0.95 | |
100 mM Cl- | +0.4 | 89.35 | 4.15 × 104 | 4.88 × 101 | 3.67 × 10-5 | 0.89 | 2.61 × 10-4 | 0.90 |
+0.45 | 94.55 | 3.09 × 103 | 2.17 × 101 | 6.63 × 10-5 | 0.91 | 3.39 × 10-5 | 0.93 | |
+0.025 | 55.43 | 1.79 × 106 | 1.14 × 104 | 8.06 × 10-6 | 0.28 | 1.61 × 10-5 | 0.94 | |
100 mM Cl- | +0.4 | 52.1 | 4.09 × 104 | 2.09 × 104 | 1.39 × 10-5 | 0.33 | 1.12 × 10-5 | 0.95 |
2 wt% GL | +0.45 | 53.63 | 7.70 × 103 | 2.15 × 104 | 2.63 × 10-4 | 0.32 | 1.30 × 10-5 | 0.93 |
+0.5 | 50.37 | 1.33 × 104 | 1.57 × 103 | 6.91 × 10-3 | 1.00 | 1.93 × 10-5 | 0.88 |
Fig. 7 Passivation behavior of rebar steel in pH 12.5 solution with 100 × 10-3 mol/L chloride addition characterized by electrochemical techniques: a potentiostatic plots, b Nyquist plots, c Mott-Schottky plots
Fig. 8 Passivation behavior of rebar steel in pH 12.5 solution with 2 wt% glycerol and 100 × 10-3 mol/L chloride additions characterized by electrochemical techniques: a potentiostatic plots, b Nyquist plots, c Mott-Schottkey plots
pH 12.5 | Polarization (VAg/AgCl) | Passivation kinetic exponent | Charge carrier density (cm-3) | Flat band potential (VAg/AgCl) |
---|---|---|---|---|
Control | +0.025 | 0.679 | 4.97 × 1020 | -0.76 |
+0.6 | 0.6171 | 2.77 × 1020 | -0.40 | |
+0.65 | 0.244 | 3.06 × 1020 | -0.49 | |
+0.025 | 0.605 | 7.51 × 1020 | -0.81 | |
100 mM Cl- | +0.4 | 0.628 | 2.31 × 1020 | -0.42 |
+0.45 | 0.635 | 6.92 × 1023 | -3.99 | |
+0.025 | 0.782 | 4.53 × 1020 | -0.77 | |
100 mM Cl- | +0.4 | 0.71 | 3.06 × 1020 | -0.63 |
2 wt% GL | +0.45 | 0.524 | 3.18 × 1020 | -0.67 |
+0.5 | 0.382 | 1.24 × 1021 | -0.88 |
Table 2 Passivation kinetic exponents and Mott-Schottky analysis from experiments at pH 12.5
pH 12.5 | Polarization (VAg/AgCl) | Passivation kinetic exponent | Charge carrier density (cm-3) | Flat band potential (VAg/AgCl) |
---|---|---|---|---|
Control | +0.025 | 0.679 | 4.97 × 1020 | -0.76 |
+0.6 | 0.6171 | 2.77 × 1020 | -0.40 | |
+0.65 | 0.244 | 3.06 × 1020 | -0.49 | |
+0.025 | 0.605 | 7.51 × 1020 | -0.81 | |
100 mM Cl- | +0.4 | 0.628 | 2.31 × 1020 | -0.42 |
+0.45 | 0.635 | 6.92 × 1023 | -3.99 | |
+0.025 | 0.782 | 4.53 × 1020 | -0.77 | |
100 mM Cl- | +0.4 | 0.71 | 3.06 × 1020 | -0.63 |
2 wt% GL | +0.45 | 0.524 | 3.18 × 1020 | -0.67 |
+0.5 | 0.382 | 1.24 × 1021 | -0.88 |
pH 9.0 | Polarization (VAg/AgCl) | Passivation kinetic exponent | Charge carrier density (Region 1) (cm-3) | Flat band potential (Region 1) (VAg/AgCl) | Charge carrier density (Region 2) (cm-3) | Flat band potential (Region 2) (VAg/AgCl) |
---|---|---|---|---|---|---|
Control | +0.025 | 0.372 | 3.59 × 1020 | -0.34 | - | - |
+0.7 | 0.719 | 2.92 × 1020 | -0.42 | 1.07 × 1020 | 0.13 | |
+0.75 | 0.991 | 1.56 × 1020 | -0.36 | 6.59 × 1019 | 0.12 | |
+0.025 | 0.366 | 3.10 × 1020 | -0.33 | - | - | |
0.3 mM Cl- | +0.7 | 1.089 | 3.16 × 1020 | -0.47 | 9.32 × 1019 | 0.12 |
+0.75 | 1.099 | 2.34 × 1020 | -0.38 | 9.24 × 1019 | 0.17 | |
+0.75 | 0.887 | 3.93 × 1020 | -0.01 | - | - | |
+0.025 | 0.533 | 3.77 × 1020 | -0.33 | - | - | |
0.3 mM Cl- 2 wt%GL | +0.65 | 0.953 | 2.92 × 1020 | -0.41 | 7.32 × 1019 | 0.24 |
+0.7 | 1.068 | 3.12 × 1020 | -0.42 | 7.76 × 1019 | 0.25 | |
+0.75 | 0.94 | 2.17 × 1020 | -0.37 | 8.77 × 1019 | 0.14 |
Table 3 Passivation kinetic exponents and Mott-Schottky analysis for experiments at pH 9.0
pH 9.0 | Polarization (VAg/AgCl) | Passivation kinetic exponent | Charge carrier density (Region 1) (cm-3) | Flat band potential (Region 1) (VAg/AgCl) | Charge carrier density (Region 2) (cm-3) | Flat band potential (Region 2) (VAg/AgCl) |
---|---|---|---|---|---|---|
Control | +0.025 | 0.372 | 3.59 × 1020 | -0.34 | - | - |
+0.7 | 0.719 | 2.92 × 1020 | -0.42 | 1.07 × 1020 | 0.13 | |
+0.75 | 0.991 | 1.56 × 1020 | -0.36 | 6.59 × 1019 | 0.12 | |
+0.025 | 0.366 | 3.10 × 1020 | -0.33 | - | - | |
0.3 mM Cl- | +0.7 | 1.089 | 3.16 × 1020 | -0.47 | 9.32 × 1019 | 0.12 |
+0.75 | 1.099 | 2.34 × 1020 | -0.38 | 9.24 × 1019 | 0.17 | |
+0.75 | 0.887 | 3.93 × 1020 | -0.01 | - | - | |
+0.025 | 0.533 | 3.77 × 1020 | -0.33 | - | - | |
0.3 mM Cl- 2 wt%GL | +0.65 | 0.953 | 2.92 × 1020 | -0.41 | 7.32 × 1019 | 0.24 |
+0.7 | 1.068 | 3.12 × 1020 | -0.42 | 7.76 × 1019 | 0.25 | |
+0.75 | 0.94 | 2.17 × 1020 | -0.37 | 8.77 × 1019 | 0.14 |
Fig. 9 Passivation behavior of rebar steel in pH 9.0 solution with no chloride addition characterized by electrochemical techniques: a potentiostatic plots, b Nyquist plots, c Mott-Schottky plots
pH 9.0 | Polarization (VAg/AgCl) | Rsoln (ohm) | Rp (ohm) | Rf (ohm) | Qp (S sn) | N | Qf (S sm) | M |
---|---|---|---|---|---|---|---|---|
Control | +0.025 | 540.9 | 9.19 × 105 | 1.79 × 105 | 1.26 × 10-8 | 0.31 | 2.76 × 10-5 | 0.90 |
+0.7 | 532 | 2.23 × 106 | 7.34 | 8.95 × 10-7 | 0.27 | 1.52 × 10-5 | 0.87 | |
+0.75 | 548.3 | 1.13 × 106 | 142.6 | 1.68 × 10-5 | 0.76 | 3.69 × 10-6 | 1.00 | |
+0.025 | 500.2 | 3.76 × 105 | 8.95 × 105 | 4.67 × 10-5 | 1.00 | 2.52 × 10-5 | 0.91 | |
0.3 mM Cl- | +0.7 | 559.8 | 4.38 × 105 | 2.25 × 104 | 2.34 × 10-5 | 0.64 | 1.72 × 10-5 | 0.85 |
+0.75 | 555 | 5.66 × 106 | 3.19 × 105 | 5.67 × 10-6 | 1.00 | 1.89 × 10-5 | 0.86 | |
+0.8 | 555.9 | 1.91 × 102 | 593.1 | 6.31 × 10-2 | 1.00 | 2.54 × 10-5 | 0.81 | |
+0.025 | 497.1 | 2.64 × 105 | 1.08 × 106 | 2.63 × 10-5 | 0.57 | 2.73 × 10-5 | 0.91 | |
0.3 mM Cl- | +0.65 | 505.4 | 2.00 × 105 | 5.30 × 105 | 4.56 × 10-5 | 1.00 | 1.65 × 10-5 | 0.84 |
2 wt%GL | +0.7 | 527.2 | 8.69 × 104 | 3.40 × 105 | 9.60 × 10-5 | 1.00 | 1.77 × 10-5 | 0.84 |
+0.75 | 532.6 | 2.71 × 103 | 1.31 × 103 | 1.65 × 10-5 | 1.00 | 7.41 × 10-6 | 0.97 |
Table 4 Equivalent electrical circuit analysis of EIS data for experiments at pH 9.0
pH 9.0 | Polarization (VAg/AgCl) | Rsoln (ohm) | Rp (ohm) | Rf (ohm) | Qp (S sn) | N | Qf (S sm) | M |
---|---|---|---|---|---|---|---|---|
Control | +0.025 | 540.9 | 9.19 × 105 | 1.79 × 105 | 1.26 × 10-8 | 0.31 | 2.76 × 10-5 | 0.90 |
+0.7 | 532 | 2.23 × 106 | 7.34 | 8.95 × 10-7 | 0.27 | 1.52 × 10-5 | 0.87 | |
+0.75 | 548.3 | 1.13 × 106 | 142.6 | 1.68 × 10-5 | 0.76 | 3.69 × 10-6 | 1.00 | |
+0.025 | 500.2 | 3.76 × 105 | 8.95 × 105 | 4.67 × 10-5 | 1.00 | 2.52 × 10-5 | 0.91 | |
0.3 mM Cl- | +0.7 | 559.8 | 4.38 × 105 | 2.25 × 104 | 2.34 × 10-5 | 0.64 | 1.72 × 10-5 | 0.85 |
+0.75 | 555 | 5.66 × 106 | 3.19 × 105 | 5.67 × 10-6 | 1.00 | 1.89 × 10-5 | 0.86 | |
+0.8 | 555.9 | 1.91 × 102 | 593.1 | 6.31 × 10-2 | 1.00 | 2.54 × 10-5 | 0.81 | |
+0.025 | 497.1 | 2.64 × 105 | 1.08 × 106 | 2.63 × 10-5 | 0.57 | 2.73 × 10-5 | 0.91 | |
0.3 mM Cl- | +0.65 | 505.4 | 2.00 × 105 | 5.30 × 105 | 4.56 × 10-5 | 1.00 | 1.65 × 10-5 | 0.84 |
2 wt%GL | +0.7 | 527.2 | 8.69 × 104 | 3.40 × 105 | 9.60 × 10-5 | 1.00 | 1.77 × 10-5 | 0.84 |
+0.75 | 532.6 | 2.71 × 103 | 1.31 × 103 | 1.65 × 10-5 | 1.00 | 7.41 × 10-6 | 0.97 |
Fig. 10 Passivation behavior of rebar steel in pH 9.0 solutions with 0.3 × 10-3 mol/L chloride addition characterized by electrochemical techniques: a potentiostatic plots, b Nyquist plots, c Mott-Schottky plots
Fig. 11 Passivation behavior of rebar steel in pH 9.0 solution with 2 wt% glycerol and 0.3 × 10-3 mol/L chloride additions characterized by electrochemical techniques: a potentiostatic scans, b Nyquist plots, c Mott-Schottky plots
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