不同pH值模拟混凝土孔隙液中钢筋钝化电化学响应与机制

张盼盼; 刘国建; 佘伟; 刘志勇; 张宇; 张云升

不同pH值模拟混凝土孔隙液中钢筋钝化电化学响应与机制

张盼盼¹,
刘国建^1,,
佘伟²,
刘志勇²,
张宇³,
张云升^{2, 3}

1.
苏州科技大学土木工程学院, 苏州215011
2.
东南大学材料科学与工程学院, 南京211189
3.
兰州理工大学土木工程学院, 兰州730050

基金项目: 国家自然科学基金(52008284)

详细信息

通讯作者:
刘国建，男，博士，副教授，硕士生导师，主要研究方向为严酷环境下钢筋混凝土锈蚀

中图分类号: TB333
计量
- 文章访问数: 18
- HTML全文浏览量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2024-08-14
- 修回日期: 2024-09-25
- 录用日期: 2024-10-01
- 网络出版日期: 2024-10-16

Electrochemical response and mechanism of steel rebar passivation in simulated concrete pore solutions with different pH values

1.
School of Civil Engineering, Suzhou University of Science and Technology, Suzhou 215011, China
2.
School of Materials Science and Engineering, Southeast University, Nanjing 211189, China
3.
School of Civil Engineering,Lanzhou University of Technology, Lanzhou 730050, China

Funds: National Natural Science Foundation of China (52008284)

摘要

摘要: 本研究旨在探讨普通低碳钢在不同pH值的混凝土孔隙溶液中的钝化行为及其机制。通过开路电位、线性极化电阻、电化学阻抗谱以及ToF-SIMS分析，深入探究了pH值对低碳钢钝化行为的影响。结果表明，在pH值较低的CH溶液中，极化电阻(R_p)缓慢增加最终稳定在120 kΩ·cm²，腐蚀电流密度(I_corr)保持在较高水平0.15 μA/cm²。表明CH溶液对低碳钢钝化效果不明显；而在pH值较高的ST溶液中，电容电抗弧一天内发生明显变化，表明其在一天内即发生钝化。且无论混凝土模拟液的pH值如何，低碳钢均能自发形成钝化膜，其表面钝化膜都经历了从快速初始生长到后期逐渐稳定的过程。pH值是促进低碳钢钝化的关键因素且与钝化膜性能存在正相关性，CH溶液中，钝化膜厚度从最初的1.930 nm上升至3.733 nm。而在ST溶液中一天内从4.786 nm增至9.187 nm，说明随着模拟液pH值的升高，钝化膜厚度为增加的趋势，形成更加稳定的钝化膜，从而使其钝化性能得到增强。
- 低碳钢 /
- 钝化 /
- pH值 /
- 电化学 /
- 混凝土
Abstract: This study aims to investigate the passivation behavior and mechanisms of low carbon steel in concrete pore solutions with different pH values. Through open circuit potential, linear polarization resistance, electrochemical impedance spectroscopy and ToF-SIMS analysis, the effect of pH on the passivation behavior of low carbon steel was examined in detail. The results demonstrate that mild steel can spontaneously form a passivation film in concrete pore solutions of any pH value, with the film on its surface undergoing a transition from rapid initial growth to a more gradual stabilization over time. pH is a crucial factor in promoting the passivation of mild steel and shows a positive correlation with the performance of the passivation film. As the pH of the simulated solution increases, there is a tendency for the thickness of the passivation film to increase, resulting in the formation of a more stable passivation layer, thereby enhancing its passivation properties.
- low carbon steel /
- passivation /
- pH values /
- electrochemical /
- concrete

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图 1 钢试样在 CH、LC 和 ST 溶液钝化阶段的腐蚀电位曲线

Figure 1. Corrosion potential curves of steel specimens in the passivation stage of CH, LC and ST solutions.

The y-axis shows the corrosion potential (E_corr) in volts (V), indicating the material’s tendency to corrode. More negative values of Ecorr suggest a higher corrosion tendency

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图 2 钢试样在CH、LC和ST溶液钝化阶段的R_p和I_corr曲线：(a)R_p；(b)I_corr

Figure 2. R_p and I_corr curves of steel specimens in the passivation stage of CH, LC and ST solutions: (a) R_p; (b) I_corr

(a) Polarization resistance (R_p) in ohms (Ω), indicating the material’s resistance to corrosion. Higher R_p suggests better corrosion resistance. (b) Corrosion current density (I_corr) in µA/cm², reflecting the rate of corrosion. Higher I_corr indicates a faster corrosion rate.

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图 3 钢试样钝化阶段的Nyquist图、Bode图和Phase图及其在CH、LC和ST溶液中的等效电路拟合结果

Figure 3. Nyquist, Bode and Phase plots of steel specimens in passivation phase and their equivalent circuit fitting results in CH, LC and ST solutions

Zi: The negative imaginary part of the impedance, representing the capacitive behavior of the system. A larger value indicates higher capacitive reactance. Zr: The real part of the impedance, representing the resistive component of the system. Higher values suggest greater resistance to current flow. |Z|: The absolute value of the impedance, which combines both the real and imaginary components. It reflects the overall opposition to the flow of current in the system

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图 4 等效电路图

Figure 4. Equivalent circuit diagram

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图 5 CH，ST模拟液中的普通低碳钢试样钝化7天的 ToF-SIMS 结果，(a)：CH，(b)：ST

Figure 5. ToF-SIMS results of normal mild steel specimens passivated for 7 days in CH and ST simulation solution. (a): CH, (b): ST

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图 6 碱溶液中钢筋的钝化过程示意图：(a)初始状态；(b)Fe(OH)₂的形成；(c)继续氧化及钝化膜的双层结构

Figure 6. Schematic representation of the passivation process of steel bars in alkali solution: (a) initial state; (b) formation of Fe(OH)₂; (c) continued oxidation and bilayer structure of passivation film

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表 1 钢筋成分表

Table 1. Chemical composition of steel bars

Element	C	Si	Mn	S	P	Fe
Wt.%	0.2	0.55	1.42	0.028	0.026	97.776

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表 2 EIS数据拟合结果

Table 2. Fitting results of EIS data of steel specimens

		$ {R}_{S} $(Ω·cm²)	CPE1,$ Q $ (S·secⁿ·cm⁻²)	CPE1,$ a $ [0<a<1]	$ {R}_{1} $ (Ω·cm²)	CPE2,$ Q $ (S·secⁿ·cm⁻²)	CPE2,$ a $ [0<a<1]	$ {R}_{ct} $ (Ω·cm²)	Chi-squared
CH	0 d	30.99	0.000181	0.8801	3524	0.00007947	0.6681	37950	1. 62E-03
	1 d	34.79	0.0006243	1	4439	0.0001044	0.6391	79980	4.18E-03
	2 d	30.94	0.0001127	0.8815	5494	0.00004949	0.6548	117700	4.44E-04
	3 d	33.37	0.0001092	0.8853	4838	0.00004493	0.6353	155900	6.45E-04
	4 d	32.86	0.0002026	0.8861	5367	0.00004023	0.6493	186520	5.36E-04
	5 d	29.14	0.0009702	0.8869	6947	0.00003695	0.6698	225400	4.11E-04
	6 d	31.38	0.0001019	0.8840	7993	0.00003565	0.6095	218800	7.27E-04
	7 d	29.54	0.0009796	0.8898	7881	0.00003274	0.6943	284900	5.77E-04
	8 d	30.53	0.0009453	0.8914	7976	0.00002633	0.6764	316300	1.07E-04
	9 d	33.21	0.0008241	0.9017	7023	0.00002888	0.6980	367900	1.69E-03
	10 d	31	0.0008867	0.8954	8369	0.0000271	0.6853	338700	1.67E-03
LC	0 d	26.88	0.00007963	0.9061	68810	0.0001285	0.8469	55570	1.76E-03
	1 d	29.81	0.00008169	0.9162	49580	0.00003099	0.8537	80470	3.31E-03
	2 d	27.02	0.00008597	0.9147	34970	0.00003930	0.8694	96460	1.57E-03
	3 d	27.35	0.00007808	0.9202	35500	0.00001436	0.9261	71310	8.15E-04
	4 d	28.73	0.00007633	0.9234	25330	0.00001419	0.8907	78030	1.06E-04
	5 d	29.51	0.00003119	1	13280	0.00005319	0.8801	1417000	1.18E-03
	6 d	26.56	0.00007546	0.9189	29240	0.00001400	0.8347	1114000	1.39E-03
	7 d	26.03	0.00007776	0.9115	37020	0.00002071	0.8937	704000	1.58E-03
	8 d	29.48	0.00007773	0.9123	31290	0.00001734	0.8714	2148000	4.01E-03
	9 d	30.64	0.00007588	0.9165	21900	0.00001732	0.9250	4468000	1.22E-03
	10 d	30.25	0.00007609	0.9173	23960	0.000018	0.8852	7130000	6.82E-04
ST	0 d	38.06	0.00007504	0.9183	54850	0.0000255	0.2326	686100	9.78E-04
	1 d	33.09	0.00003052	1	15580	0.00005107	0.8384	619000	1.38E-03
	2 d	30.92	0.00003169	1	25560	0.00004324	0.8214	656700	1.84E-03
	3 d	29.45	0.00002717	1	12940	0.00005259	0.8538	741300	5.99E-04
	4 d	33.62	0.00002766	1	13730	0.00004696	0.8482	846000	9.22E-04
	5 d	34.40	0.00007253	0.9229	14380	0.00001506	0.8328	562500	1.20E-04
	6 d	35.79	0.00002826	1	14090	0.00004813	0.8487	988800	4.91E-04
	7 d	38.06	0.00007504	0.9183	14850	0.00003524	0.8326	6861000	9.78E-04
	8 d	38.24	0.00002682	1	12490	0.00005017	0.8504 0.85	1237000	7.70E-04
	9 d	31.27	0.00007871	0.9116	13360	0.00005955	0.7915	1256000	7.13E-04
	10 d	34.21	0.00004021	1	18620	0.00001925	0.7912	1145000	6.35E-03
Notes: R_s: Solution resistance. CPE1, Q1: Constant phase element 1 (CPE), describing the non-ideal capacitance behavior. CPE1, n1: Exponent of CPE1, indicating deviation from ideal capacitive behavior. R₁: Charge transfer resistance. CPE2, Q2: Constant phase element 2 (CPE), associated with surface processes. CPE2, n2: Exponent of CPE2, indicating deviation from ideal capacitive behavior. R_ct: Corrosion resistance. Chi-squared: Indicator of the goodness-of-fit for the model.)

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表 3 钝化阶段钝化膜厚度计算(nm)

Table 3. Calculation of passivation film thickness (nm) at passivation stage

	0 d	1 d	2 d	3 d	4 d	5 d	6 d	7 d	8 d	9 d	10 d
CH	2.16	2.252	2.681	2.536	2.693	2.795	2.884	3.287	3.564	3.629	3.757
LC	2.412	2.699	3.285	3.997	3.869	3.789	3.854	3.905	3.881	3.798	3.773
ST	3.572	4.379	4.317	4.296	4.271	4.165	4.137	4.364	4.152	4.312	4.288

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