Please wait a minute...
Acta Metall Sin  2019, Vol. 55 Issue (4): 457-468    DOI: 10.11900/0412.1961.2018.00475
Current Issue | Archive | Adv Search |
Influence of SO42- on the Corrosion Behavior of Q235B Steel Bar in Simulated Pore Solution
Kaiqiang LI1,Lujia YANG2,Yunze XU1(),Xiaona WANG3,Yi HUANG1
1. School of Naval Architecture & Ocean Engineering, Dalian University of Technology, Dalian 116024, China
2. School of Innovation and Entrepreneurship, Dalian University of Technology, Dalian 116024, China
3. School of Physics and Optoelectronic Engineering, Dalian University of Technology, Dalian 116024, China
Download:  HTML  PDF(12674KB) 
Export:  BibTeX | EndNote (RIS)      
Abstract  

Cl- and SO42- are most common aggressive ions containing in the seawater which may cause the localized corrosion of reinforcement structures. It is found that a protective passive film will form on the steel surface in the concrete pore solution. The localized breakdown of the passive film caused by the aggressive ions and the carbonation are the main reason for the localized corrosion initiation of reinforcements. In the previous studies, it is found that the performances of the SO42- on the rebar corrosion were quite different in different pH value conditions and the test results did not unify. Therefore, the influence of pH value and the SO42- on the corrosion behavior of Q235B carbon steel in the simulated pore solution was studied using anodic polarization, electrochemical impedance spectra (EIS), Mott-Schottky (M-S) and potentiostatic polarization methods. The anodic polarization curves indicate that when the pH value of the simulated pore solution was higher than 11, SO42- had no damage to the passive film. However, once the pH value of the simulated pore solution decreased to 10, a small amount of SO42- can lead to the breakdown of the passive film and induce pitting initiation. EIS and M-S measurement results suggest that the stability of the passive film would decrease with the decreasing of the solution pH. The concentration of the defect would increase in the passive film due to the pH decrease. The stability reduction and the increase of defect concentration both can lead to the passive film become fragile and more easily to be destroyed by SO42-. Through the potentiostatic polarization test in conjunction with SEM observation, it is found that SO42- can inhibit the growth of the passive film during the initial film formation period and lead to the appearance of metastable pitting corrosion under high pH value conditions. In the low pH value conditions, SO42- could accumulate at the defect of the passive film and lead to stable pitting propagate on the steel surface.

Key words:  Q235B steel      passive film      SO42-      pitting corrosion     
Received:  16 October 2018     
ZTFLH:  O646  
Fund: National Science and Technology Pillar Program during the Thirteenth Five-Year Plan Period(No.2016ZX05057)
Corresponding Authors:  Yunze XU     E-mail:  xuyunze123@163.com

Cite this article: 

Kaiqiang LI, Lujia YANG, Yunze XU, Xiaona WANG, Yi HUANG. Influence of SO42- on the Corrosion Behavior of Q235B Steel Bar in Simulated Pore Solution. Acta Metall Sin, 2019, 55(4): 457-468.

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2018.00475     OR     https://www.ams.org.cn/EN/Y2019/V55/I4/457

Test groupPre-passivation conditionpH value of thetest solution

SO42- concentration

mol·L-1

ANo pre-passivation12.60
BNo pre-passivation12.60.1
C4 h pre-passivation in pH=12.6 pore solution without SO42-12.60.1
DNo pre-passivation10.00
ENo pre-passivation10.00.1
F4 h pre-passivation in pH=10 pore solution without SO42-10.00.1
Table 1  The test groups of the constant voltage polarization measurements
Fig.1  The anodic polarization curves of Q235B steel under different SO42- concentration in the simulated pore solution with pH=12.6 (a), 12.0 (b), 11.0 (c) and 10.0 (d) (i—current density, E—voltage)
Fig.2  The Nyquist plots (a, c, e, g) and Bode plots (b, d, f, h) of Q235B steel in the simulated pore solution with pH=12.6 (a, b), 12.0 (c, d), 11.0 (e, f) and 10.0 (g, h)
Fig.3  Equivalent circuit for EIS measurement results fitting shown in Fig.2 (Rs—solution resistance, Rf—film resistance, CPE—constant phase angle element)
Fig.4  The main fitting results of EIS measurement (Y0—admittance of film capacitance, n—dispersion coefficient, Rf—film resistance, R2—coefficient of determination) (a) fitted Y0 (b) fitted n (c) fitted Rf
Fig.5  
pHVfb / mVND / (1021 cm-3)
12.6-8082.24
12.0-6852.66
11.0-5123.04
10.0-4103.73
Table 2  M-S fitting results under different pH values simulated pore solution
Fig.6  The current noise variation of the electrodes in the test groups A~C as shown in Table 1 (I—current noise, t—test duration. Insets show the magnified curves)(a) A-1 (b) A-2 (c) B-1 (d) B-2 (e) C-1 (f) C-2
Fig.7  The electrode SEM images of the surface morphology in the groups A~C after test(a) A-1 (b) A-2 (c) B-1 (d) B-2 (e) C-1 (f) C-2
Fig.8  The current noise variation of the electrodes in the test groups D~F as shown in Table 1 (Insets show the magnified curves)(a) D-1 (b) D-2 (c) E-1 (d) E-2 (e) F-1 (f) F-2
Fig.9  The electrodes SEM image of the surface morphology in the groups D~F after test(a) D-1 (b) D-2 (c) E-1 (d) E-2 (e) F-1 (f) F-2
1 Cao Y H, Dong S G, Zheng D J, et al. Multifunctional inhibition based on layered double hydroxides to comprehensively control corrosion of carbon steel in concrete [J]. Corros. Sci., 2017, 126: 166
2 Ales C, Kosec T, Legat A. Characterization of steel corrosion in mortar by various electrochemical and physical techniques [J]. Corros. Sci., 2013, 75: 47
3 Valipour M, Shekarchi M, Ghods P. Comparative studies of experimental and numerical techniques in measurement of corrosion rate and time-to-corrosion-initiation of rebar in concrete in marine environments [J]. Cem. Concr. Compos., 2014, 48: 98
4 Tan Y J. Experimental methods designed for measuring corrosion in highly resistive and inhomogeneous media [J]. Corros. Sci., 2011, 53: 1145.
5 Chakri S, Frateur I, Orazem M E, et al. Improved EIS analysis of the electrochemical behaviour of carbon steel in alkaline solution [J]. Electrochim. Acta, 2017, 246: 924.
6 Mundra S, Criado M, Bernal S A, et al. Chloride-induced corrosion of steel rebars in simulated pore solutions of alkali-activated concretes [J]. Cem. Concr. Res., 2017, 100: 385
7 Qiao B, Du R G, Chen W, et al. Effect of NO2- and Cl- on the corrosion behavior of reinforcing steel in simulated concrete pore solutions [J]. Acta Metall. Sin., 2010, 46: 245
7 乔 冰, 杜荣归, 陈 雯等. NO2-和Cl-对模拟混凝土孔隙液中钢筋腐蚀行为的影响 [J]. 金属学报, 2010, 46: 245
8 Kumar M P, Mini K M, Rangarajan M. Ultrafine GGBS and calcium nitrate as concrete admixtures for improved mechanical properties and corrosion resistance [J]. Constr. Build. Mater., 2018, 182: 249
9 Angst U, Elsener B, Larsen C K, et al. Critical chloride content in reinforced concrete—A review [J]. Cem. Concr. Res., 2009, 39: 1122
10 Ann K Y, Song H W. Chloride threshold level for corrosion of steel in concrete [J]. Corros. Sci., 2007, 49: 4113
11 Jin Z Q, Zhao X, Zhao T J, et al. Effect of Ca(OH)2, NaCl, and Na2SO4 on the corrosion and electrochemical behavior of rebar [J]. Chin. J. Oceanol. Limnol., 2017, 35: 681
12 Ghods P, Isgor O B, McRae G, et al. The effect of concrete pore solution composition on the quality of passive oxide films on black steel reinforcement [J]. Cem. Concr. Compos., 2009, 31: 2
13 El Aal E E A, El Wanees S A, Diab A, et al. Environmental factors affecting the corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under natural corrosion conditions [J]. Corros. Sci., 2009, 51: 1611
14 El Haleem S M A, El Wanees S A, El Aal E E A, et al. Environmental factors affecting the corrosion behavior of reinforcing steel II. Role of some anions in the initiation and inhibition of pitting corrosion of steel in Ca(OH)2 solutions [J]. Corros. Sci., 2010, 52: 292
15 El Haleem S M A, El Wanees S A, Bahgat A. Environmental factors affecting the corrosion behaviour of reinforcing steel. V. Role of chloride and sulphate ions in the corrosion of reinforcing steel in saturated Ca(OH)2 solutions [J]. Corros. Sci., 2013, 75: 1
16 Liu G J, Zhang Y S, Ni Z W, et al. Corrosion behavior of steel submitted to chloride and sulphate ions in simulated concrete pore solution [J]. Constr. Build. Mater., 2016, 115: 1
17 Al-Amoudi O S B, Maslehuddin M. The effect of chloride and sulfate ions on reinforcement corrosion [J]. Cem. Concr. Res., 1993, 23: 139
18 Al-Amoudi O S B, Rasheeduzzafar A A, Maslehuddin M, et al. Influence of sulfate ions on chloride-induced reinforcement corrosion in Portland and blended cement concretes [J]. Cem. Concr. Aggreg., 1994, 16(1): 3
19 Shaheen F, Pradhan B. Effect of chloride and conjoint chloride-sulfate ions on corrosion of reinforcing steel in electrolytic concrete powder solution (ECPS) [J]. Constr. Build. Mater., 2015, 101: 99
20 Shaheen F, Pradhan B. Influence of sulfate ion and associated cation type on steel reinforcement corrosion in concrete powder aqueous solution in the presence of chloride ions [J]. Cem. Concr. Res., 2017, 91: 73
21 Williamson J, Isgor O B. The effect of simulated concrete pore solution composition and chlorides on the electronic properties of passive films on carbon steel rebar [J]. Corros. Sci., 2016, 106: 82
22 Yang L J, Xu Y Z, Zhu Y S, et al. Evaluation of interaction effect of sulfate and chloride ions on reinforcements in simulated marine environment using electrochemical methods [J]. Int. J. Electrochem. Sci., 2016, 52: 6943
23 Xu Y Z, He L M, Yang L J, et al. Electrochemical study of steel corrosion in saturated calcium hydroxide solution with chloride ions and sulfate ions [J]. Corrosion, 2018, 74: 1063
24 Vigneshwaran K K K, Permeh S, Echeverría M, et al. Corrosion of post-tensioned tendons with deficient grout, part 1: Electrochemical behavior of steel in alkaline sulfate solutions [J]. Corrosion, 2018, 74: 362
25 Ai Z Y, Jiang J Y, Sun W, et al. Enhanced passivation of alloy corrosion-resistant steel Cr10Mo1 under carbonation—Passive film formation, the kinetics and mechanism analysis [J]. Cem. Concr. Compos., 2018, 92: 178
26 Ai Z Y, Jiang J Y, Sun W, et al. Passive behaviour of alloy corrosion-resistant steel Cr10Mo1 in simulating concrete pore solutions with different pH [J]. Appl. Surf. Sci., 2016, 389: 1126
27 Sánchez M, Gregori J, Alonso C, et al. Electrochemical impedance spectroscopy for studying passive layers on steel rebars immersed in alkaline solutions simulating concrete pores [J]. Electrochim. Acta, 2007, 52: 7634
28 Chakri S, Frateur I, Orazem M E, et al. Improved EIS analysis of the electrochemical behaviour of carbon steel in alkaline solution [J]. Electrochim. Acta, 2017, 246: 924
29 Saremi M, Mahallati E. A study on chloride-induced depassivation of mild steel in simulated concrete pore solution [J]. Cem. Concr. Res., 2002, 32: 1915
30 Li Y, Cheng Y F. Passive film growth on carbon steel and its nanoscale features at various passivating potentials [J]. Appl. Surf. Sci., 2017, 396: 144
31 Chen W, Du R G, Ye C Q, et al. Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques [J]. Electrochim. Acta, 2010, 55: 5677
32 Sato N. Anodic breakdown of passive films on metals [J]. J. Electrochem. Soc., 1982, 129: 255
33 El Haleem S M A, El Aal E E A, El Wanees S A, et al. Environmental factors affecting the corrosion behaviour of reinforcing steel: I. The early stage of passive film formation in Ca(OH)2 solutions [J]. Corros. Sci., 2010, 52: 3875
34 Freire L, Nóvoa X R, Montemor M F, et al. Study of passive films formed on mild steel in alkaline media by the application of anodic potentials [J]. Mater. Chem. Phys., 2009, 114: 962
35 Morrison S R. Electrochemistry at semiconductor and oxidized metal electrodes [M]. New York: Plenum Press, 1980: 416
36 MacDonald D D. The history of the point defect model for the passive state: A brief review of film growth aspects [J]. Electrochim. Acta, 2011, 56: 1761
37 Dong Z H, Shi W, Guo X P. Initiation and repassivation of pitting corrosion of carbon steel in carbonated concrete pore solution [J]. Corros. Sci., 2011, 56: 5890
38 Lu Y F, Dong J H, Ke W. Effects of SO42- on the corrosion behavior of NiCu Low alloy steel in deaerated bicarbonate solutions [J]. Acta Metall. Sin., 2015, 51: 1067
38 卢云飞, 董俊华, 柯 伟. SO42-对NiCu低合金钢在除氧NaHCO3溶液中腐蚀行为的影响 [J]. 金属学报, 2015, 51: 1067
39 Niu L B, Nakada K. Effect of chloride and sulfate ions in simulated boiler water on pitting corrosion behavior of 13Cr steel [J]. Corros. Sci., 2015, 96: 171
40 Kolics A, Polkinghorne J C, Wieckowski A. Adsorption of sulfate and chloride ions on aluminum [J]. Electrochim. Acta, 1998, 43: 2605
[1] FENG Hao,LI Huabing,LU Pengchong,YANG Chuntian,JIANG Zhouhua,WU Xiaolei. Investigation on Microbiologically Influenced Corrosion Behavior of CrCoNi Medium-Entropy Alloy byPseudomonas Aeruginosa[J]. 金属学报, 2019, 55(11): 1457-1468.
[2] Jiang XU, Xike BAO, Shuyun JIANG. In Vitro Corrosion Resistance of Ta2N Nanocrystalline Coating in Simulated Body Fluids[J]. 金属学报, 2018, 54(3): 443-456.
[3] Dahai XIA, Shizhe SONG, Jianqiu WANG, Jingli LUO. Research Progress on Sulfur-Induced Corrosion of Alloys 690 and 800 in High Temperature and High Pressure Water[J]. 金属学报, 2017, 53(12): 1541-1554.
[4] Yongjun CHEN, Xiaogang HU, Jianbing QIANG, Chuang DONG. QUASICRYSTAL ABRASIVE POLISHING ON SOFT METALS VIA A CHARACTERISTIC SMEARING WEAR MECHANISM FOR EFFICIENT SURFACE FLATTENING, HARDENING AND CORROSION ENHANCEMENT[J]. 金属学报, 2016, 52(10): 1353-1362.
[5] Nan PIAO,Ji CHEN,Chengjiang YIN,Cheng SUN,Xinghang ZHANG,Zhanwen WU. INVESTIGATION ON PITTING CORROSION BEHAVIOR OF ULTRAFINE-GRAINED 304L STAINLESS STEEL IN Cl- CONTAINING SOLUTION[J]. 金属学报, 2015, 51(9): 1077-1084.
[6] Haiwei HUANG, Zhenbo WANG, Li LIU, Xingping YONG, Ke LU. FORMATION OF A GRADIENT NANOSTRUCTURED SURFACE LAYER ON A MARTENSITIC STAINLESS STEEL AND ITS EFFECTS ON THE ELECTRO- CHEMICAL CORROSION BEHAVIOR[J]. 金属学报, 2015, 51(5): 513-518.
[7] CHEN Wenjuan, HAO Long, DONG Junhua, KE Wei, WEN Huailiang. EFFECT OF pH VALUE ON THE CORROSION EVOLUTION OF Q235B STEEL IN SIMULATED COASTAL-INDUSTRIAL ATMOSPHERES[J]. 金属学报, 2015, 51(2): 191-200.
[8] CHEN Wenjuan, HAO Long, DONG Junhua, KE Wei, WEN Huailiang. EFFECT OF SO2 ON CORROSION EVOLUTION OF Q235B STEEL IN SIMULATED COASTAL-INDUSTRIAL ATMOSPHERE[J]. 金属学报, 2014, 50(7): 802-810.
[9] XIN Sensen, LI Moucheng, SHEN Jianian. EFFECT OF TEMPERATURE AND CONCENTRATION RATIO ON PITTING RESISTANCE OF 316L STAINLESS STEEL IN SEAWATER[J]. 金属学报, 2014, 50(3): 373-378.
[10] WANG Binbin,WANG Zhenyao,CAO Gongwang,LIU Yanjie,KE Wei. LOCALIZED CORROSION OF ALUMINUM ALLOY 2024 EXPOSED TO SALT LAKE ATMOSPHERIC ENVIRONMENT IN WESTERN CHINA[J]. 金属学报, 2014, 50(1): 49-56.
[11] WANG Changgang, DONG Junhua, KE Wei, LI Xiaofang. INVESTIGATION ON PITTING CORROSION BEHAVIOR OF COPPER IN THE MIXED SOLUTION OF HCO3-, SO42- AND Cl-[J]. 金属学报, 2013, 49(2): 207-213.
[12] SUN Feilong, LI Xiaogang, LU Lin, CHENG Xuequn, DONG Chaofang, GAO Jin. CORROSION BEHAVIOR OF 5052 AND 6061 ALUMINUM ALLOYS IN DEEP OCEAN ENVIRONMENT OF SOUTH CHINA SEA[J]. 金属学报, 2013, 49(10): 1219-1226.
[13] WU Zhanwen, CHEN Ji, PIAO Nan, YANG Mingchuan. SYNTHESIS AND PASSIVE PROPERTY OF NANOCOMPOSITE Ni-WC COATING[J]. 金属学报, 2013, 49(10): 1185-1190.
[14] TAN Yu LIANG Kexin ZHANG Shenghan. SEMICONDUCTOR PROPERTIES OF THE PASSIVE FILM FORMED ON Ni201 IN NEUTRAL SOLUTION[J]. 金属学报, 2012, 48(8): 971-976.
[15] WEI Xin, DONG Junhua, TONG Jian, ZHENG Zhi,KE Wei. INFLUENCE OF TEMPERATURE ON PITTING CORROSION RESISTANCE OF Cr26Mo1 ULTRA PURE HIGH CHROMIUM FERRITE STAINLESS STEEL IN 3.5%NaCl SOLUTION[J]. 金属学报, 2012, 48(4): 502-507.
No Suggested Reading articles found!