Passive Behavior of Corrosion-Resistant Cr-Containing Steel Bars in Simulated High-Alkaline Concrete Pore Solution

doi:10.11900/0412.1961.2023.00203

Acta Metall Sin

2025, Vol. 61

Issue (6): 929-940 DOI: 10.11900/0412.1961.2023.00203

Research paper

Current Issue | Archive | Adv Search

Passive Behavior of Corrosion-Resistant Cr-Containing Steel Bars in Simulated High-Alkaline Concrete Pore Solution

WANG Muliang¹^,², SUN Yupeng¹^,², CHEN Lei¹^,², WEI Jie²(

), DONG Junhua²(

)

1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

Cite this article:

WANG Muliang, SUN Yupeng, CHEN Lei, WEI Jie, DONG Junhua. Passive Behavior of Corrosion-Resistant Cr-Containing Steel Bars in Simulated High-Alkaline Concrete Pore Solution. Acta Metall Sin, 2025, 61(6): 929-940.

Download:

HTML

PDF(3363KB)
Export: BibTeX | EndNote (RIS)

Abstract

Reinforced concrete has become the preferred choice for modern building structures owing to its long durability, strong structure, flexible, and diverse designs, wide availability, and low cost. Traditional carbon steel bars are prone to corrosion in marine environments, resulting in problems such as steel bar breakage and concrete cracks, thereby affecting the safety and reliability of marine engineering structures. Therefore, using high-performance corrosion-resistant alloy steel bars can effectively solve the problem of steel corrosion in marine engineering and improve the durability and maintainability of engineering structures. Concrete is a highly alkaline environment when it is free from erosion, and the pH value of its pore solution is 12.5-13.6. When steel bars are exposed to this environment, a stable passive film forms on their surface. This spontaneously formed passive film can keep the steel bars in a passive state, preventing corrosion and considerably extending the service life of reinforced concrete structures. The differences in the composition and structure of the passive film on steel bars represent important reasons for the different corrosion resistance performances of steel bars in concrete. To study the passive behavior of corrosion-resistant rebars (20MnSi steel, 3Cr steel, and 9Cr steel) with different Cr contents (0, 3%, and 9%, mass fraction) in simulated high-alkaline concrete pore solution, electrochemical measurements (including open circuit potential, electrochemical impedance spectroscopy, polarization curve, and Mott-Schottky curve) were used to study the changes in the properties of the passive film on the surface of the rebars over time. XPS was used to analyze the composition and structure of the passive film. The results show that a passive layered film was formed on the surface of the rebars in the simulated high-alkaline concrete pore solution, and the structure, composition, and protective properties of the passive film were closely related to the Cr content and passivation time of the rebars. The passive film of 20MnSi steel was mainly composed of Fe(III) compounds in the outer layer and Fe(II) oxides in the inner layer. The outer layer of the passive film of 3Cr steel and 9Cr steel comprised Fe(III) and Cr(III) oxides and hydroxides, and the inner layer comprised Fe(II) oxides and Cr(III) compounds. The passive films formed by the three types of rebars exhibited n-type semiconductor properties within the potential range of -0.8 to 0.2 V (vs SCE). As the immersion time increased, the defect density in the passive film decreased, leading to decreased corrosion current density of the rebars and improved corrosion resistance. When the Cr content is increased, the point defect density of the passive film decreases. At the same time, the passive film becomes dense, resulting in improved corrosion resistance of the rebars.

Key words: corrosion-resistant steel bar concrete simulating solution passive film electrochemical test

Received: 06 May 2023

ZTFLH:

TG174

Fund: Major Research and Development Project of Liaoning Province(2020JH1/10100001)

Corresponding Authors: WEI Jie, associate professor, Tel: 13478204310, E-mail: jwei@imr.ac.cn;
DONG Junhua, professor, Tel: 13842056525, E-mail: jhdong@imr.ac.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	WANG Muliang
	SUN Yupeng
	CHEN Lei
	WEI Jie
	DONG Junhua

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2023.00203 OR https://www.ams.org.cn/EN/Y2025/V61/I6/929

Table 1 Nominal compositions of 20MnSi, 3Cr, and 9Cr steels

Fig.1 SEM images of three kinds of steel bars after annealing heat treatment
(a) 20MnSi steel (b) 3Cr steel (c) 9Cr steel

Fig.2 Open circuit potential (E_ocp) of 20MnSi, 3Cr, and 9Cr steels with immersion time in simulated concrete pore solution (SCE—saturated calomel electrode)

Fig.3 Polarization curves of three steels in simulated concrete pore solution for different immersion time (E—potential, i—current density)

Fig.4 Corrosion current density (i_corr) of 20MnSi, 3Cr, and 9Cr steels in simulated concrete pore solution for different immersion time

Fig.5 Bode-impedance modulus (|Z|) plots (a1-a3) and Bode-phase angle plots (b1-b3) of 20MnSi (a1, b1), 3Cr (a2, b2), and 9Cr (a3, b3) steels in simulated solution for different immersion time

Fig.6 Equivalent electrical circuit model for EIS data fitting (R_s—solution resistance, R_c—polarization resistance of cathodic oxygen reduction, Q_c—cathode oxygen reduction capacitance, R_a—charge transfer resistance, Q_a—double layer capacitance)

Table 2 Equivalent circuit parameters of 20MnSi, 3Cr, and 9Cr steels after different immersion time

Fig.7 Evolutions of R_c (a) and R_a (b) of 20MnSi, 3Cr, and 9Cr steels with time

Fig.8 Mott-Schottky (MS) curves of three steels in simulated concrete pore solution for different immersion time (C_sc—capacitance of space charge layer)
(a) 20MnSi steel
(b) 3Cr steel
(c) 9Cr steel

Table 3 Point defect densities of 20MnSi, 3Cr, and 9Cr steels in simulated concrete pore solution after different immersion time

Fig.9 Detailed XPS of the surface passive film formed on the 20MnSi (a), 3Cr (b, d) and 9Cr (c, e) steels with different sputter depths after immersion of 168 h

Fig.10 Depth trend of element contents of three steel specimens
(a) 20MnSi steel (b) 3Cr steel (c) 9Cr steel

Fig.11 Distribution of different components with sputter depth within the passive film of 20MnSi (a, b), 3Cr (c, d) and 9Cr (e, f) after 24 h (a, c, e) and 168 h (b, d, f) immersion in simulated concrete pore solutions

Fig.12 Schematics of growth mechanism of the passive film formed on three steels in simulated concrete pore solution
(a) initial growth stage of 20MnSi steel passive film
(b) stable stage of 20MnSi steel passive film
(c) initial growth stage of passive film for 3Cr and 9Cr steels
(d) stable stage of passive film for 3Cr and 9Cr steels

1	Pang L, Li Q W. Service life prediction of RC structures in marine environment using long term chloride ingress data: Comparison between exposure trials and real structure surveys [J]. Constr. Build. Mater., 2016, 113: 979
2	Guo A X, Li H T, Ba X, et al. Experimental investigation on the cyclic performance of reinforced concrete piers with chloride-induced corrosion in marine environment [J]. Eng. Struct., 2015, 105: 1
3	Jin W L, Zhao Y X. Durability of Concrete Structures [M]. 2nd Ed., Beijing: Science Press, 2014: 15
	金伟良, 赵羽习. 混凝土结构耐久性 [M]. 第2版. 北京: 科学出版社, 2014: 15
4	Coombes M A, La Marca E C, Naylor L A, et al. Getting into the groove: Opportunities to enhance the ecological value of hard coastal infrastructure using fine-scale surface textures [J]. Ecol. Eng., 2015, 77: 314
5	Morris W, Vazquez M. Corrosion of reinforced concrete exposed to marine environment [J]. Corros. Rev., 2002, 20: 469
6	Wang X H, Gao Y. Corrosion behavior of epoxy-coated reinforced bars in RC test specimens subjected to pre-exposure loading and wetting-drying cycles [J]. Constr. Build. Mater., 2016, 119: 185
7	Hou B R. The Cost of Corrosion in China [M]. Beijing: Science Press, 2017: 497
	侯保荣. 中国腐蚀成本 [M]. 北京: 科学出版社, 2017: 497
8	Ke W. Investigation Report on Corrosion in China [M]. Beijing: Chemical Industry Press, 2003: 22
	柯伟. 中国腐蚀调查报告 [M]. 北京: 化学工业出版社, 2003: 22
9	Bertolini L, Elsener B, Pedeferri P, et al. Corrosion of Steel in Concrete: Prevention, Diagnosis, Repair [M]. 2nd Ed., Weinheim: John Wiley & Sons, 2013: 172
10	Feng Z C, Cheng X Q, Dong C F, et al. Passivity of 316L stainless steel in borate buffer solution studied by Mott-Schottky analysis, atomic absorption spectrometry and X-ray photoelectron spectroscopy [J]. Corros. Sci., 2010, 52: 3646
11	Uemura M, Yamamoto T, Fushimi K, et al. Depth profile analysis of thin passive films on stainless steel by glow discharge optical emission spectroscopy [J]. Corros. Sci., 2009, 51: 1554
12	Vetter K J, Gorn F. Kinetics of layer formation and corrosion processes of passive iron in acid solutions [J]. Electrochim. Acta, 1973, 18: 321
13	Abreu C M, Cristóbal M J, Losada R, et al. Comparative study of passive films of different stainless steels developed on alkaline medium [J]. Electrochim. Acta, 2004, 49: 3049
14	Veleva L, Alpuche-Aviles M A, Graves-Brook M K, et al. Comparative cyclic voltammetry and surface analysis of passive films grown on stainless steel 316 in concrete pore model solutions [J]. J. Electroanal. Chem., 2002, 537: 85
15	Veleva L, Alpuche-Aviles M A, Graves-Brook M K, et al. Voltammetry and surface analysis of AISI 316 stainless steel in chloride-containing simulated concrete pore environment [J]. J. Electroanal. Chem., 2005, 578: 45
16	Alvarez S M, Bautista A, Velasco F. Corrosion behaviour of corrugated lean duplex stainless steels in simulated concrete pore solutions [J]. Corros. Sci., 2011, 53: 1748
17	Volpi E, Olietti A, Stefanoni M, et al. Electrochemical characterization of mild steel in alkaline solutions simulating concrete environment [J]. J. Electroanal. Chem., 2015, 736: 38
18	Liu M, Cheng X Q, Li X G, et al. Corrosion behavior of Cr modified HRB400 steel rebar in simulated concrete pore solution [J]. Constr. Build. Mater., 2015, 93: 884
19	Ghods P, Isgor O B, Bensebaa F, et al. Angle-resolved XPS study of carbon steel passivity and chloride-induced depassivation in simulated concrete pore solution [J]. Corros. Sci., 2012, 58: 159
20	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
21	Cao C N. Principles of Electrochemistry of Corrosion [M]. 2nd Ed., Beijing: Chemical Industry Press, 2004: 34
	曹楚南. 腐蚀电化学原理 [M]. 第2版. 北京: 化学工业出版社, 2004: 34
22	Xue F, Wei X, Dong J H, et al. Effect of chloride ion on corrosion behavior of low carbon steel in 0.1 M NaHCO₃ solution with different dissolved oxygen concentrations [J]. J. Mater. Sci. Technol., 2019, 35: 596
23	Martínez I, Andrade C. Application of EIS to cathodically protected steel: Tests in sodium chloride solution and in chloride contaminated concrete [J]. Corros. Sci., 2008, 50: 2948
24	Luo H, Dong C F, Xiao Ket al. Characterization of passive film on 2205 duplex stainless steel in sodium thiosulphate solution [J]. Appl. Surf. Sci., 2011, 258: 631
25	Yao J Z, Macdonald D D, Dong C F. Passive film on 2205 duplex stainless steel studied by photo-electrochemistry and ARXPS methods [J]. Corros. Sci., 2019, 146: 221
26	Hamadou L, Kadri A, Benbrahim N. Characterisation of passive films formed on low carbon steel in borate buffer solution (pH 9.2) by electrochemical impedance spectroscopy [J]. Appl. Surf. Sci., 2005, 252: 1510
27	Liu L, Li Y, Wang F H. Pitting corrosion behavior of a sputtered nanocrystalline thin film of austenitic stainless steel in 3.5 mass% NaCl solution [J]. Corros. Sci. Prot. Technol., 2010, 22: 283
	刘莉, 李瑛, 王福会. 奥氏体不锈钢溅射纳米晶薄膜的点蚀行为研究 [J]. 腐蚀科学与防护技术, 2010, 22: 283
28	Jiang J Y, Wang D Q, Chu H Y, et al. The passive film growth mechanism of new corrosion-resistant steel rebar in simulated concrete pore solution: Nanometer structure and electrochemical study [J]. Materials, 2017, 10: 412
29	Donik Č, Kocijan A, Grant J T, et al. XPS study of duplex stainless steel oxidized by oxygen atoms [J]. Corros. Sci., 2009, 51: 827
30	Freire L, Carmezim M J, Ferreira M G S, et al. The passive behaviour of AISI 316 in alkaline media and the effect of pH: A combined electrochemical and analytical study [J]. Electrochim. Acta, 2010, 55: 6174
31	Mesquita T J, Chauveau E, Mantel M, et al. A XPS study of the Mo effect on passivation behaviors for highly controlled stainless steels in neutral and alkaline conditions [J]. Appl. Surf. Sci., 2013, 270: 90
32	Yuan X W, Wang X, Cao Y, et al. Natural passivation behavior and its influence on chloride-induced corrosion resistance of stainless steel in simulated concrete pore solution [J]. J. Mater. Res. Technol., 2020, 9: 12378

[1]	ZHAO Pingping, SONG Yingwei, DONG Kaihui, HAN En-Hou. Synergistic Effect Mechanism of Different Ions on the Electrochemical Corrosion Behavior of TC4 Titanium Alloy[J]. 金属学报, 2023, 59(7): 939-946.
[2]	TANG Yanbing, SHEN Xinwang, LIU Zhihong, QIAO Yanxin, YANG Lanlan, LU Daohua, ZOU Jiasheng, XU Jing. Corrosion Behaviors of Selective Laser Melted Inconel 718 Alloy in NaOH Solution[J]. 金属学报, 2022, 58(3): 324-333.
[3]	LV Chenxi, SUN Yangting, CHEN Bin, JIANG Yiming, LI Jin. Influence of Potentionstatic Pulse Technique on Pitting Behavior and Pitting Resistance of 317L Stainless Steel[J]. 金属学报, 2021, 57(12): 1607-1613.
[4]	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[J]. 金属学报, 2019, 55(4): 457-468.
[5]	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.
[6]	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.
[7]	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.
[8]	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.
[9]	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.
[10]	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.
[11]	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.
[12]	ZHAO Bo DU Cuiwei LIU Zhiyong LI Xiaogang YANG Jike LI Yueqiang. CORROSION BEHAVIOR OF X80 STEEL IN YINGTAN SOIL SIMULATED SOLUTION UNDER DISBONDED COATING[J]. 金属学报, 2012, 48(12): 1530-1536.
[13]	ZHU Xuemei CAO Xuemei LIU Ming LEI Mingkai ZHANG Yansheng. AN ANTIFERROMAGNETIC Fe24Mn4Al5Cr COVAR ALLOY IMPULSE--PASSIVATED BY AN ALTERNATING CURRENT VOLTAGE OVERLAPPING A DIRECT CURRENT VOLTAGE AND ITS CORROSION RESISTANCE[J]. 金属学报, 2012, 48(11): 1357-1364.
[14]	HUANG Fa WANG Jianqiu HAN En-Hou KE Wei. EFFECTS OF Cl^- CONCENTRATION AND TEMPERATURE ON THE CORROSION BEHAVIOR OF ALLOY 690 IN BORATE BUFFER SOLUTION[J]. 金属学报, 2011, 47(7): 809-815.
[15]	XIANG Hongliang HUANG Weilin LIU Dong HE Fushan. EFFECTS OF N CONTENT ON MICROSTRUCTURE AND PROPERTIES OF 29Cr CASTING SUPER DUPLEX STAINLESS STEEL[J]. 金属学报, 2010, 46(3): 304-310.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed