硅酸盐学报

模拟混凝土孔隙液碱性环境对Cr10Mo合金钢钝化行为的影响

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张伦馨 ¹ , 刘国建 ¹ , 刘志勇 ² , 佘伟 ² , 张云升 ²^,³

硅酸盐学报 | 研究论文 2025,53(2): 339-348

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硅酸盐学报 |研究论文 2025 , 53 (2) : 339 -348

模拟混凝土孔隙液碱性环境对Cr10Mo合金钢钝化行为的影响

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张伦馨¹, 刘国建¹, 刘志勇², 佘伟², 张云升²^,³

作者信息

^1．苏州科技大学土木工程学院，江苏苏州 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

通讯作者:

刘国建（1986—），男，博士，副教授。

作者简介:

张伦馨（1999—），男，硕士研究生。

Effect of Alkaline Environment in Simulated Concrete Pore Solution on Passivation Behavior of Cr10Mo Alloy Steel

Lunxin ZHANG¹, Guojian LIU¹, Zhiyong LIU², Wei SHE², Yunsheng ZHANG²^,³

Affiliations

^1.School of Civil Engineering, Suzhou University of Science and Technology, Suzhou 215011, Jiangsu, 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

Corresponding Author:

LIU Guojian (1986-), male, Ph.D., Associate Professor. E-mail: liuguojiande@gmail.com

ZHANG Lunxin (1999-), male, Master candidate. E-mail: zhanglunxin1999@163.com

出版时间: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240216

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摘要

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矿物掺合料的掺入导致混凝土孔隙溶液pH值波动，进而影响钢筋表面钝化膜稳定性与耐腐蚀性。本工作旨在探讨Cr10Mo合金钢在不同pH值的模拟混凝土孔隙液中的钝化行为及其演变规律。通过开路电位、线性极化电阻和电化学阻抗谱、Pourbaix分析，深入研究了pH值对Cr10Mo合金钢钝化过程的影响。研究发现：无论在哪种pH值条件下，合金钢均可自发形成由内层Cr₂O₃和外层Fe₂O₃构成的梯度钝化膜。随着溶液pH值降低，钝化膜中Cr氧化物/氢氧化物含量增加，从而使膜结构更加致密稳定。合金钢的钝化性能随着pH值的降低而增强，主要归因于不同pH值环境下Cr（OH）₃向Cr₂O₃或的选择性转化。

关键词

合金钢 / 钝化 / pH值 / 模拟混凝土孔隙液 / 电化学

Abstract

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Introduction

As the issue of steel corrosion in reinforced concrete structures becomes increasingly severe, enhancing their durability has become crucial. Therefore, the application of highly corrosion resistant steel, such as stainless steel and corrosion resistant alloy steel, is an effective countermeasure. However, the durability of steel in concrete is influenced by numerous factors, and its corrosion mechanisms exhibit long term and complex characteristics. The use of simulated concrete pore solution methods in research simplifies influencing factors and shortens the research cycle, thus being widely applied in academic studies. In modern construction practices, to meet low carbon and environmental requirements, a large amount of mineral admixtures is often added to cement. However, the use of these admixtures can cause fluctuations in the pH value of the concrete pore solution, thereby affecting the stability of the passivation film on the steel surface and increasing the risk of steel corrosion. Therefore, this study aims to investigate the passivation behavior and evolution of Cr10Mo alloy steel in simulated concrete pore solutions with different pH values.

Methods

Steel was machined using a controlled lathe to produce rebar electrode discs with a diameter of 16 mm and a thickness of 10 mm. The bottom surface of the rebar was used as the working surface, with a working area of 2.01 cm². All other non-working surfaces were sealed with epoxy resin. Each experiment utilized three rebar electrode discs as parallel samples. The working surfaces were gradually polished to a mirror finish using 400 #, 800 #, 1200 # and 2000 # silicon carbide sandpaper, then cleaned with deionized water, followed by an alcohol wash to remove grease. After drying, the discs were immediately placed into the standard corrosion cell. This procedure was repeated to polish a total of nine rebar electrode discs.

The electrochemical measurements were conducted using a classical three electrode system. The rebar electrode served as the working electrode, the saturated calomel electrode was used as the reference electrode, and a platinum electrode was employed as the auxiliary electrode. All measurements were performed at a laboratory temperature of 20 ℃. The parameters selected for the linear polarization resistance test were as follows: the scanning potential was ±10 mV vs. OCP, and the scanning rate was 10 mV/min. The EIS test parameters were as follows: the perturbation voltage was a sine wave signal with an amplitude of 10 mV, and the scanning frequency range was from 10 mHz to 100 kHz.

Results and discussion

The OCP and LPR test results indicate that in the CH simulated solution with the lowest pH value, alloy steel exhibits the lowest corrosion tendency after passivation. In the higher pH LC solution, corrosion tendency slightly increases, while in the highest pH ST solution, it is the highest. The R_p and I_c_orr values are as follows: CH solution at 1100 kΩ·cm² and 0.047 μA/cm², LC solution at 806 kΩ·cm² and 0.064 μA/cm², and ST solution at 534 kΩ·cm² and 0.097 μA/cm². Thus, the passivation performance ranks as CH > LC > ST, indicating that lower pH conditions lead to a more stable passivation film, effectively preventing further corrosion. EIS and equivalent circuit fitting results show that the CH simulation has the best passivation effect, with its α value and R_ct value surpassing those of the LC and ST simulated solutions, highlighting its superior passivation performance. Additionally, the electrochemical behavior of the rebar samples in different environments reveals that the integrity and electrochemical protection capability of the passivation film are closely related to the pH value. Comprehensive investigations, including Pourbaix diagrams, Gibbs free energy analysis, and the passivation reaction process of chromium, indicate that the selective transformation of Cr(OH)₃ to Cr₂O₃ or in the passivation film influences its stability at lower pH values. Specifically, at lower pH values, Cr(OH)₃ tends to convert to Cr₂O₃, forming a denser passivation film, thereby enhancing the passivation performance of the alloy steel. Conversely, under higher pH conditions, some Cr(OH)₃ may convert to the less stable , leading to a decrease in the stability of the passivation film and weakening its protective effect.

Conclusions

Regardless of the pH conditions, alloy steel can spontaneously form a gradient passivation film consisting of an inner layer of Cr₂O₃ and an outer layer of Fe₂O₃. As the solution pH decreases, the content of Cr oxides/hydroxides in the passivation film increases, resulting in a denser and more stable film structure. The passivation performance of the alloy steel improves with decreasing pH value, primarily due to the selective transformation of Cr(OH)₃ to Cr₂O₃ or in different pH environments. At lower pH values, the I_corr of alloy steel significantly decreases, and R_p significantly increases, indicating better formation and stability of the passivation film. In different pH simulated solutions, the passivation performance of the alloy steel follows the order: pH 12.4(CH) > pH 12.9(LC) > pH 13.5(ST).

Key words

alloy steel / passivation / pH values / simulated concrete pore solutions / electrochemical

引用本文

张伦馨, 刘国建, 刘志勇, 佘伟, 张云升. 模拟混凝土孔隙液碱性环境对Cr10Mo合金钢钝化行为的影响. 硅酸盐学报, 2025 , 53 (2) : 339 -348 . DOI: 10.14062/j.issn.0454-5648.20240216

Lunxin ZHANG, Guojian LIU, Zhiyong LIU, Wei SHE, Yunsheng ZHANG. Effect of Alkaline Environment in Simulated Concrete Pore Solution on Passivation Behavior of Cr10Mo Alloy Steel[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (2) : 339 -348 . DOI: 10.14062/j.issn.0454-5648.20240216

基金

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国家自然科学基金(52008284)

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2025年第53卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240216

接收时间：2024-03-16
首发时间：2026-10-22
出版时间：2025-02-20

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收稿日期：2024-03-16
修回日期：2024-05-29

基金

国家自然科学基金(52008284)

作者信息

^1．苏州科技大学土木工程学院，江苏苏州 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

通讯作者:

刘国建（1986—），男，博士，副教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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