Corrosion Inhibition Behavior of 1-Hydroxyethylidene-1, 1-Diphosphonic Acid on 20SiMn Steel in Simulated Concrete Pore Solution Containing Cl-
CAO Fengting1,2, WEI Jie1, DONG Junhua1(), KE Wei1, WANG Tiegang2, FAN Qixiang2
1.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China 2.Tianjin Key Laboratory of High Speed Cutting and Precision Machining, School of Mechanical Engineering, Tianjin University of Technology and Education, Tianjin 300222, China
Cite this article:
CAO Fengting, WEI Jie, DONG Junhua, KE Wei, WANG Tiegang, FAN Qixiang. Corrosion Inhibition Behavior of 1-Hydroxyethylidene-1, 1-Diphosphonic Acid on 20SiMn Steel in Simulated Concrete Pore Solution Containing Cl-. Acta Metall Sin, 2020, 56(6): 898-908.
The corrosion of steel rebar in concrete will be induced once the passive film is destroyed by chlorides or carbonation. Several techniques have been employed to reduce the corrosion so far. Among them, adding inhibitors is effective one because of its advantages, such as high efficiency and easy handling. 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), a typical organic phosphonic acid, is a low toxic corrosion inhibitor for steel and iron in neutral aerobic environment. This compound was first used as scale inhibitor in water treatment industry, such as cooling water circulation system. The molecule of HEDP has two phosphate groups, making it a powerful chelating ability with metallic ions. However, most of the current studies of HEDP focus on neutral or near-neutral systems, and there are few reports on the corrosion inhibition of steel reinforcement in alkaline environment. Therefore, it is not clear whether HEDP can play the role of corrosion inhibitor by protecting the passive film and resist foreign corrosive Cl-. In this work, the inhibition effect of HEDP towards 20SiMn steel was investigated in simulated concrete pore solution contaminated by Cl- (Sat.Ca(OH)2+1 mol/L NaCl) by electrochemical methods (corrosion potential, potentiodynamic polarization curves, EIS and Mott-Schottcky curves) and surface analysis techniques (SEM, XPS). The results showed that HEDP was a mixed inhibitor and its inhibition efficiency increased first and then decreased with the increase of concentration, the optimal concentration is 1.441×10-4 mol/L . At the optimal concentration, HEDP could obviously enlarge the passive region, prolong the passive period of 20SiMn steel from 6 h to 9 h , and improve the charge-transfer resistance significantly with the inhibition efficiency around 46.45%~59.78%. When pitting corrosion occurs, HEDP could hinder its development with the inhibition efficiency over 93%. The inhibition mechanism was the preferential adsorption of HEDP over Cl- by forming a complete adsorption film outside the passive film of the steel.
Fund: National Natural Science Foundation of China(U1867216);National Natural Science Foundation of China(51501201);National Natural Science Foundation of China(51801219)
Fig.1 Potentiodynamic polarization curves of 20SiMn steel in 1 mol/L NaCl saturated Ca(OH)2 solution with different concentrations of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) (E—potential, i—current density)
Fig.2 EIS of 20SiMn steel in 1 mol/L NaCl saturated Ca(OH)2 solution with different concentrations of HEDP (a) Nyquist plots (b) Bode-impedance modulus plots (c) Bode-phase angle plots
Fig.3 EIS of 20SiMn steel immersed in 1 mol/L NaCl saturated Ca(OH)2 solution (a) Nyquist plots (Inset shows the enlarged Nyquist plots at 9 and 24 h) (b) Bode-impedance modulus plots (c) Bode-phase angle plots
Fig.4 EIS of 20SiMn steel immersed in 1 mol/L NaCl saturated Ca(OH)2 solution with 1.441×10-4 mol/L HEDP (a) Nyquist plots (b) Bode-impedance modulus plots (c) Bode-phase angle plots
Fig.5 The equivalent circuits used to fit the EIS of passive stage (a), and pitting corrosion stage without (b) and with (c) inductance arc (Rs—the solution resistance, Qf—the constant phase element (CPE) of the film, Rf —the resistance of passive film, Qct—the CPE of the electric double layer, Rct—the charge transfer resistance, L—the equivalent inductance of pitting corrosion, RL—the equivalent resistance of pitting corrosion)
HEDP
mol·L-1
Time
h
Rs
Ω·cm2
Qf-Y0
10-4 F·cm-2
nf
Rf
104 Ω·cm2
Qct-Y0
10-5 F·cm-2
nct
Rct
105 Ω·cm2
L
105 H·cm2
RL
103 Ω·cm2
η
%
0
0.5
4.50
1.68
1.00
0.12
4.35
0.91
1.66
-
3
3.82
1.52
0.98
0.23
4.08
0.92
2.09
-
6
3.83
1.56
0.97
0.26
3.89
0.93
1.83
-
9
3.84
1.24
1.00
0.10
4.28
0.92
0.09
-
24
2.99
0.46
0.92
0.07
14.78
0.57
0.05
1.54
9.62
-
1.441×10-4
0.5
4.26
1.10
0.87
0.81
4.73
0.94
3.10
46.45
3
2.91
0.91
0.87
1.59
4.45
0.94
3.97
47.36
6
3.82
0.76
0.86
2.54
4.47
0.96
4.55
59.78
9
3.77
0.75
0.86
3.33
4.00
0.96
7.12
98.74
24
3.95
0.44
0.85
0.39
1.87
0.66
0.76
93.42
Table 1 Fitting results of EIS of 20SiMn steel at different immersion time in 1 mol/L NaCl saturated Ca(OH)2 solution without and with 1.441×10-4 mol/L HEDP
Fig.6 Curves of Rf and Rct of 20SiMn steel with immersion time in 1 mol/L NaCl saturated Ca(OH)2 solution without and with 1.441×10-4 mol/L HEDP
Fig.7 Corrosion potentials (Ecorr) of 20SiMn steel immersed in 1 mol/L NaCl saturated Ca(OH)2 solution without and with 1.441×10-4 mol/L HEDP
Fig.8 SEM images of 20SiMn steel observed after removal of corrosion products immersed for 7 h in 1 mol/L NaCl saturated Ca(OH)2 solution without (a) and with (b) 1.441×10-4 mol/L HEDP
Fig.9 Mott-Schottky curves of 20SiMn steel immersed in 1 mol/L NaCl saturated Ca(OH)2 solution without and with 1.441×10-4 mol/L (CSC—capacitance of space charge layer)
Fig.10 Deconvoluted XPS spectra of Cl2p (a), P2p (b), Fe2p (c) and O1s (d) of 20SiMn steel immersed for 1 h in 1 mol/L NaCl saturated Ca(OH)2 solution without and with 1.441×10-4 mol/L HEDP
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