硅酸盐学报

水泥-矿物掺合料复合胶凝材料净浆萃取液中合金耐蚀钢筋钝化行为

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刘先超 ¹ , 艾志勇 ¹^,²^,³ , 黎星琪 ¹ , 张骏卿 ¹ , 郭晓钧 ¹ , 宋丹 ⁴

硅酸盐学报 | 研究论文 2026,54(8): 2831-2842

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硅酸盐学报 |研究论文 2026 , 54 (8) : 2831 -2842

水泥-矿物掺合料复合胶凝材料净浆萃取液中合金耐蚀钢筋钝化行为

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刘先超¹, 艾志勇¹^,²^,³, 黎星琪¹, 张骏卿¹, 郭晓钧¹, 宋丹⁴

作者信息

^1．南昌航空大学土木与交通学院，南昌 330063

^2．江西省交投养护科技集团有限公司，公路桥梁与隧道结构江西省重点实验室，南昌 330200

^3．东南大学，江苏省土木工程材料重点实验室，南京 211189

^4．河海大学力学与材料学院，南京 210098

通讯作者:

艾志勇（1987—），男，博士，副教授。

作者简介:

刘先超（2000—），男，硕士研究生。

Passivation Behavior of Alloy Corrosion Resistant Steel in Extracted Solutions from Cement-Mineral Admixture Composite Cementitious Material Pastes

Xianchao LIU¹, Zhiyong AI¹^,²^,³, Xingqi LI¹, Junqin ZHANG¹, Xiaojun GUO¹, Dan SONG⁴

Affiliations

^1.School of Civil Engineering and Transportation, Nanchang Hangkong University, Nanchang 330063, China

^2.Jiangxi Key Laboratory of Highway Bridge and Tunnel Structures, Jiangxi Jiaotou Maintenance Science and Technology Group Co. Ltd., Nanchang 330200, China

^3.Jiangsu Key Laboratory of Construction Materials, Southeast University, Nanjing 211189, China

^4.College of Mechanics and Materials, Hohai University, Nanjing 210098, China

Corresponding Author:

{AI} Zhiyong (1987-), male, Ph.D., Associate Professor. E-mail: aizhiyongyx@163.com

LIU Xianchao (2000-), male, Master candidate. E-mail: 17630175019@163.com

出版时间: 2026-07-10 doi: 10.14062/j.issn.0454-5648.20250558

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摘要

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开发使用合金耐蚀钢筋替代普通碳素钢筋，是长效解决钢筋锈蚀问题的根本方法。采用线性极化、电化学阻抗、电容-电位等方法研究了Cr10Mo1合金耐蚀钢筋（LA）[引入HRB400普通碳素钢筋（LC）对比]在不同掺量（质量分数0%、15%、30%、45%）水泥-矿物掺合料复合胶凝材料净浆萃取液中钝化行为，使用X射线光电子能谱技术分析了钢筋钝化膜组成成分及结构特征。结果表明：2种钢筋在不同净浆萃取液中均能较好致钝，钝化行为规律存在差异。矿物掺合料掺量增加时，LA钢筋钝化呈现增强趋势，而LC钢筋钝化逐步减弱。LA钢筋钝化膜为双层结构，外层主要由FeOOH/Fe（OH）₃和Fe₂O₃组成，内层主要含有Cr₂O₃、Cr（OH）₃和FeO；LC钢筋钝化膜为单层结构，主要包含Fe₂O₃、FeOOH/Fe（OH）₃和FeO。矿物掺合料掺量增加时，净浆萃取液碱度降低，LA钢筋更多Cr元素参与钝化膜形成，使其钝化增强，而LC钢筋钝化膜中Fe氧化物逐渐分解，具有较强保护作用的FeO含量降低，使其钝化减弱。研究结论证实，矿物掺合料引入对于LA钢筋钝化效果并无妨碍，但会削弱LC钢筋钝化强度。

关键词

合金耐蚀钢筋 / 矿物掺合料 / 碱度 / 钝化行为

Abstract

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Introduction

The cement industry contributes approximately 8% of global CO₂ emissions, with each ton of clinker production for releasing nearly one ton of CO₂. Mineral admixtures such as slag, fly ash, and silica fume become essential for developing sustainable concrete, enabling a partial replacement of cement (i.e., 15%-45%, mass fraction), while enhancing durability through pozzolanic reactions. However, high-volume substitutions of exceeding 30% critically depress a pore solution alkalinity from pH value 13.3 to 12.5-12.8, destabilizing passive films on conventional carbon steel (LC) and elevating corrosion risks by 3-5 times. This alkalinity reduction has severe threats to structural integrity in marine environments and deicing salt exposure, driving global infrastructure repair costs beyond $2.5 trillion annually. A Cr10Mo1 alloy corrosion-resistant steel (LA) was developed, having a chloride threshold 10 times greater than that of LC in simulated pore solutions. However, its passivation behavior in realistic cement-mineral admixture systems with synergistic interactions of Ca²⁺, SO₄^2-, and Al³⁺ ions remains unexplored. In this study, the passivation mechanisms of the steel in complex paste extracts were investigated to provide foundational data for designing durable and sustainable infrastructure.

Methods

The passivation kinetics were analyzed by electrochemical techniques like linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), and Mott-Schottky analysis. The LA and LC electrodes (φ10 mm×10 mm) were polished to a 2000-grit finish and immersed for 10 d in extracts derived from cement pastes containing different mineral admixtures of 0%, 15%, 30%, and 45% (slag/fly ash = 1∶1), designated as 0SF, 15SF, 30SF, and 45SF. The paste extracts were prepared with P·O 42.5 cement at a water-to-binder ratio of 1∶1, cured at 25 ℃ for 14 d, filtered through 0.45 μm membranes, and stored in nitrogen to prevent carbonation. The measured pH values reduced progressively from 13.4 (0SF) to 12.5 (45SF). Electrochemical testing utilized a three-electrode cell with a platinum counter electrode and a saturated calomel reference electrode (SCE). LPR scans (±20 mV vs. open-circuit potential at 0.166 7 mV/s) and EIS measurements (10 mV amplitude, 0.01-1.00×10⁴ Hz frequency range) were conducted after passivation. The Mott-Schottky analysis was performed at 1000 Hz with potential sweeps from -1.5 V to +0.25 V vs. SCE (50 mV/s). Equivalent circuit modeling (R_s-[CPE_dl-R_ct]-[CPE_f-R_f]) was used to fit the EIS data to resolve solution resistance (R_s), passive film properties (CPE₁, R₁), and charge transfer resistance (CPE₂, R₂). X-ray photoelectron spectroscopy (XPS) was used to characterize compositional gradients by an Axis Ultra DLD spectrometer with Al K_α radiation (1486.6 eV) and Ar⁺ sputtering (0.02 nm/s). The spectra of Fe 2p₃/₂ and Cr 2p₃/₂ were deconvoluted via the Gaussian-Lorentzian peak fitting.

Results and Discussion

The steels of LA and LC both can be effectively passivated in all extracts, while demonstrating fundamentally divergent responses to increasing mineral admixture content. The LA displays significantly an enhanced passivation, evidenced by an 81% increase in polarization resistance (i.e., R_p: 348 kΩ·cm² in 0SF to 630 kΩ·cm² in 45SF) and a positive shift in corrosion potential (i.e., E_corr: -157 mV to -128 mV). Conversely, the LC suffers a degraded passivity with a 54% reduction in R_p (i.e., 348 kΩ·cm² to 160 kΩ·cm²) and a negative E_corr shift to -208 mV. The Nyquist plots corroborate these results, revealing expanded capacitive arcs for the LA and contracted arcs for the LC in low-pH value extracts. The charge transfer resistance (R_ct) for the LA increases from 5.4×10⁵ Ω·cm² (0SF) to 6.4×10⁵ Ω·cm² (45SF), which is decreased by 44% (i.e., from 5.9×10⁵ Ω·cm² in 0SF to 3.3×10⁵ Ω·cm² in 45SF) for the LC. The Mott-Schottky analysis further distinguishes their electronic properties. The LA exhibits a n-p heterojunction behavior characterized by positive slopes in the -1.00 V to +0.25 V region and negative slopes between -1.5 V and -1.0 V, with decreasing total carrier density (N_total) from 4.96×10²⁰ cm^-3 (0SF) to 1.93×10²⁰ cm^-3 (45SF). In contrast, the LC maintains a n-type semi-conductivity with increasing N_total from 4.93×10²⁰ cm^-3 to 7.09×10²⁰ cm^-3.

XPS depth profile shows critical differences in passive film architecture. The LA forms a bilayer structure comprising an outer layer (0-5 nm) of FeOOH/Fe(OH)₃ (712.2 eV) and Fe₂O₃ (710.7 eV), and an inner layer (5-15 nm) enriched with Cr₂O₃ (576.3 eV), Cr(OH)₃ (577.1 eV), and FeO (709.5 eV). Reduced alkalinity triggers an increase of 32% in Cr-oxide content (i.e., Cr_ox+hy/Cr_metal=2.8 in 45SF vs. 2.1 in 0SF), forming a dense chromium-rich barrier. The LC develops a monolayer Fe-oxide film (0-10 nm) containing Fe₂O₃, FeOOH, and FeO, with decreasing FeO content by 67% (i.e., Fe²⁺/Fe³⁺=0.18 in 45SF vs. 0.55 in 0SF). Mechanistically, a low alkalinity elevates the oxidation potential of chromium in the LA, promoting Cr³⁺ incorporation into the inner film. The resultant Cr₂O₃ (p-type semiconductor) establishes a high-energy barrier (i.e., >1.2 eV) against anion penetration, while coexisting FeO (n-type) stabilized cation transport. For the LC, FeO decomposition (Fe²⁺→Fe³⁺) at a low pH value increases oxygen vacancy density, accelerating ionic transport through the film and diminishing chloride adsorption capacity resulted from loss of [Fe²⁺-Cl^-] coordination sites.

Conclusions

Mineral admixtures content variation at 15%-45% could affect the passivation behavior of Cr10Mo1 alloy corrosion-resistant steel (LA) and ordinary carbon steel (LC). The two steels exhibited a good passivation in the paste extract solutions, but had different performances. As the amount of mineral admixture increased, the passivation of the LA enhanced, while the passivation effect of the LC gradually weakened. The passivation film of the LA was a bilayer structure, with the outer layer primarily composed of FeOOH/Fe(OH)₃ and Fe₂O₃, and the inner layer mainly consisting of Cr₂O₃, Cr(OH)₃, and FeO. The passivation film of LC was a monolayer structure, mainly containing Fe₂O₃, FeOOH/Fe(OH)₃, and FeO. The alkalinity of the paste extract solution decreased, and more Cr elements involved in the formation of the passivation film of the LA with the increase in mineral admixture content, enhancing its passivation. Meanwhile, for the LC, Fe oxides in the passivation film gradually decomposed, and the content of FeO that provided a decreased protection, leading to a weakened passivation. This study indicated that the introduction of mineral admixture could not hinder the passivation effect of the LA, but weaken the passivation strength of the LC.

Key words

alloy corrosion-resistant steel / mineral admixtures / alkalinity / passivation behavior

引用本文

刘先超, 艾志勇, 黎星琪, 张骏卿, 郭晓钧, 宋丹. 水泥-矿物掺合料复合胶凝材料净浆萃取液中合金耐蚀钢筋钝化行为. 硅酸盐学报, 2026 , 54 (8) : 2831 -2842 . DOI: 10.14062/j.issn.0454-5648.20250558

Xianchao LIU, Zhiyong AI, Xingqi LI, Junqin ZHANG, Xiaojun GUO, Dan SONG. Passivation Behavior of Alloy Corrosion Resistant Steel in Extracted Solutions from Cement-Mineral Admixture Composite Cementitious Material Pastes[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (8) : 2831 -2842 . DOI: 10.14062/j.issn.0454-5648.20250558

基金

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国家自然科学基金项目(51908257; 52278255)
江西省自然科学基金项目(20202BAB214023)
江西省“双千计划”创新领军人才长期项目(jxsq2023101099)
南昌航空大学博士启动基金项目(EA202211255)
江苏省土木工程材料重点实验室开放课题基金项目(CM2018-06)

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2026年第54卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250558

接收时间：2025-07-17
首发时间：2026-10-22
出版时间：2026-07-10

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出版历史

收稿日期：2025-07-17
修回日期：2025-08-08

基金

国家自然科学基金项目(51908257; 52278255)

江西省自然科学基金项目(20202BAB214023)

江西省“双千计划”创新领军人才长期项目(jxsq2023101099)

南昌航空大学博士启动基金项目(EA202211255)

江苏省土木工程材料重点实验室开放课题基金项目(CM2018-06)

作者信息

^1．南昌航空大学土木与交通学院，南昌 330063

^2．江西省交投养护科技集团有限公司，公路桥梁与隧道结构江西省重点实验室，南昌 330200

^3．东南大学，江苏省土木工程材料重点实验室，南京 211189

^4．河海大学力学与材料学院，南京 210098

通讯作者:

艾志勇（1987—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250558

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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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