硅酸盐学报

温-湿变化下混凝土中氯离子-硫酸根离子的耦合竞争和传输行为

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陈正 ¹^,² , 俞嘉敏 ¹^,² , 王一琛 ¹^,² , 易超凡 ¹^,²

硅酸盐学报 | 混凝土耐久性机理表征与预测方法专题—研究论文 2026,54(2): 623-640

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硅酸盐学报 |混凝土耐久性机理表征与预测方法专题—研究论文 2026 , 54 (2) : 623 -640

温-湿变化下混凝土中氯离子-硫酸根离子的耦合竞争和传输行为

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陈正¹^,², 俞嘉敏¹^,², 王一琛¹^,², 易超凡¹^,²

作者信息

^1．广西大学土木建筑工程学院，南宁 530004

^2．广西大学广西防灾减灾与工程安全重点实验室，南宁 530004

通讯作者:

易超凡（1992—），男，博士，助理教授。

作者简介:

陈正（1982—），男，博士，教授。

Coupled Competitive and Transport Behavior of Chloride-Sulphate Ions in Concrete at Different Temperatures and Humidities

Zheng CHEN¹^,², Jiamin YU¹^,², Yichen WANG¹^,², Chaofan YI¹^,²

Affiliations

^1.School of Civil Engineering and Architecture, Guangxi University, Nanning 530004, China

^2.Guangxi Key Laboratory of Disaster Prevention and Structural Safety, Guangxi University, Nanning 530004, China

Corresponding Author:

YI Chaofan (1992-), male, Ph.D., Assistant Professor. E-mail: chaofan@gxu.edu.cn

CHEN Zheng (1982-), male, Ph.D., Professor. E-mail: chenzheng@gxu.edu.cn

出版时间: 2026-02-20 doi: 10.14062/j.issn.0454-5648.20250424

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摘要

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混凝土结构在氯盐-硫酸盐耦合侵蚀作用下易发生耐久性劣化，其侵蚀过程受到服役环境中温-湿度变化的显著影响。为揭示盐-温-湿复杂条件下的氯离子-硫酸根离子耦合传输机制，建立了考虑温-湿度变化的氯离子-硫酸根离子耦合竞争传输模型，并通过试验验证了模型的可靠性和适用性。结果表明：当温度循环变化的上限值增加时，自由氯离子和总氯离子浓度显著增加，且氯离子-硫酸根离子间竞争交互作用导致的自由氯离子浓度差值[Δc（Cl-F）]和总氯离子浓度差值[Δc（Cl-T）]更为明显；而处于湿度循环时，高湿度上限将促进氯离子扩散，而低湿度环境会削弱离子间竞争交互作用对钙矾石（AFt）和弗里德尔盐（Fs）生成的抑制作用。当环境中侵蚀性离子浓度比c（SO₄^2-）/c（Cl^-）增大时，氯离子侵蚀深度减小，而竞争交互作用引起的Δc（Cl-F）显著增加；反之，提高氯离子占比会降低硫酸根离子浓度，并强化竞争交互作用对自由硫酸根离子浓度差值[Δc（S-F）]的影响。

关键词

氯离子-硫酸根离子 / 耦合传输 / 竞争交互作用 / 温度 / 湿度

Abstract

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Introduction

Concrete is a fundamental material for infrastructure in coastal and saline-alkali regions, which persistently faces a severe challenge of coupled chloride and sulphate attack. Chloride ingress induces steel corrosion, while sulphate ions lead to concrete cracking and mechanical degradation through the formation of expansive products. Under real service conditions, dynamic variations in temperature and humidity significantly affect the transport and reaction processes of these aggressive ions within concrete, resulting in complex competitive interactions between chloride and sulphate ions. Although previous research explored the transport behavior of single ions under constant environmental conditions, the synergistic migration mechanisms and competitive effects under combined salt, temperature, and humidity multi-field coupling remain inadequately understood. It is thus crucial for accurately assessing the durability and service life of concrete structures in complex environments to establish a comprehensive transport model that integrates temperature, humidity, ionic competition, and material damage.

Method

A chloride-sulphate ion transport model was proposed based on multi-species transport theory, explicitly accounting for temperature and humidity variations, ionic competition, and the evolution of material microstructure. In the model, ionic diffusion coefficients were modified via introducing a temperature-dependent function and a humidity-dependent function. A competitive correction factor was also introduced to characterize the competition between ions for diffusion pathways. Within the reaction term, a kinetic parameter was incorporated to describe the decomposition of Friedel's salt (Fs) by sulphate ions, representing the dynamic two-way competitive reaction. Furthermore, the model could account for the volumetric expansion induced by the formation of ettringite (AFt) and Fs and its subsequent impact on the pore structure and transport properties, coupled with a damage function to quantify the acceleration of transport due to cracking. Besides, natural immersion tests were conducted on mortar specimens under various conditions. The concentrations of chloride and sulphate ions at different depths were measured. Numerical simulations were performed using a software named COMSOL Multiphysics, and the simulated results were compared with the experimental data.

Results and Discussion

The model validation demonstrates a good agreement between the simulated results and experimental data with relative errors for chloride and sulphate ions of below 0.32% and 0.55%, respectively. This indicates the model's applicability under complex salt-temperature-humidity conditions. The further numerical simulations also reveal some key findings. The concentrations of both free and total chloride ions increase significantly as the upper limit of the temperature increases from 283 K to 308 K. The peak values of the competitive interaction-induced nett free chloride concentration [Δc(Cl-F)] and nett total chloride concentration [Δc(Cl-T)] reach 266.55 mol/m³ and 290.91 mol/m³, respectively, indicating that elevated temperatures intensify the competitive interaction between ions. The response of sulphate ions to temperature is less pronounced, without an increase in free concentration, although the total sulphate concentration increases with temperature. High humidity conditions (i.e., RH = 1.0) markedly promote chloride ion diffusion and the formation of corrosion products. The peak values of Δc(Cl-F) and Δc(Cl-T) increase with rising humidity. In contrast, the effect of humidity on the nett free sulphate concentration [Δc(S-F)] is relatively minor. However, humidity significantly affects the distribution of total sulphate ions, resulting in a deeper and wider peak for nett total sulphate concentration [Δc(S-T)] under a high humidity. An increase in the environmental SO₄^2-/Cl^- ratio reduces the penetration depth of chloride ions, but significantly increases Δc(Cl-F), up to 259.39 mol/m³. Conversely, increasing the Cl^-/SO₄^2- ratio reduces the sulphate ion concentration and intensifies the competitive effect on Δc(S-F), although the magnitude of this increase is lower than that occurred in the chloride system. For a 40 mm cover thickness, increasing the temperature from 283 K to 308 K reduces a predicted service life due to sulphate attack and chloride-induced corrosion from 22 a and 43 a to approximately 6 a and 7 a, respectively, compared to the associated exclusive attack. Under a coupled attack, the service lives are 11 a and 16 a, respectively, indicating that coupling retards the degradation process. Increasing relative humidity also substantially shortens the service life, highlighting a critical influence of temperature and humidity control in practical engineering.

Conclusions

This study established a numerical model that could characterize the coupled competitive transport of chloride and sulphate ions in concrete under complex salt-temperature-humidity conditions. The modelling performance was validated with a good accuracy against experimental results. The key findings were summarized as follows: 1) Elevated temperature intensified ionic competition, significantly inhibiting chloride transport, while its effect on sulphate ions was weaker; 2) High humidity promoted chloride diffusion and competitive effects, affecting the distribution of total sulphate ions; 3) Variations in the environmental ionic concentration ratio could regulate the intensity of competitive interaction, particularly affecting chloride ingress behavior; 4) The influence of temperature variation on the transport of aggressive ions was more pronounced than that of humidity, and sulphate attack played a dominant role in controlling the durability of coastal concrete structures. The proposed model could provide a theoretical tool and a design basis for durability assessment and service life prediction of concrete structures exposed to complex environments.

Key words

chloride-sulphate ions / coupled transport / competitive interaction / temperature / humidity

引用本文

陈正, 俞嘉敏, 王一琛, 易超凡. 温-湿变化下混凝土中氯离子-硫酸根离子的耦合竞争和传输行为. 硅酸盐学报, 2026 , 54 (2) : 623 -640 . DOI: 10.14062/j.issn.0454-5648.20250424

Zheng CHEN, Jiamin YU, Yichen WANG, Chaofan YI. Coupled Competitive and Transport Behavior of Chloride-Sulphate Ions in Concrete at Different Temperatures and Humidities[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (2) : 623 -640 . DOI: 10.14062/j.issn.0454-5648.20250424

基金

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国家自然科学基金青年基金项目(52408246)
广西科技重大专项(桂科AA23023034)

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2026年第54卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250424

接收时间：2025-06-03
首发时间：2026-10-27
出版时间：2026-02-20

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出版历史

收稿日期：2025-06-03
修回日期：2025-06-20

基金

国家自然科学基金青年基金项目(52408246)

广西科技重大专项(桂科AA23023034)

作者信息

^1．广西大学土木建筑工程学院，南宁 530004

^2．广西大学广西防灾减灾与工程安全重点实验室，南宁 530004

通讯作者:

易超凡（1992—），男，博士，助理教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250424

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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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