硅酸盐学报

氧化石墨烯涂覆砂增强水泥基材料抗氯离子侵蚀性能

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冯甘霖 ¹^,²^,³ , 罗盛禹 ¹ , 罗启灵 ¹^,²^,³^,⁴ , 龙武剑 ¹^,²^,³^,⁴

硅酸盐学报 | 化学外加剂助力现代混凝土绿色低碳与高性能化专题—研究论文 2025,53(3): 505-518

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硅酸盐学报 |化学外加剂助力现代混凝土绿色低碳与高性能化专题—研究论文 2025 , 53 (3) : 505 -518

氧化石墨烯涂覆砂增强水泥基材料抗氯离子侵蚀性能

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冯甘霖¹^,²^,³, 罗盛禹¹, 罗启灵¹^,²^,³^,⁴, 龙武剑¹^,²^,³^,⁴

作者信息

^1．深圳大学土木与交通工程学院，广东深圳 518060

^2．广东省滨海土木工程耐久性重点实验室，广东深圳 518060

^3．深圳市低碳建筑材料与技术重点实验室，广东深圳 518060

^4．深圳大学，深地工程智能建造与健康运维全国重点实验室，广东深圳 518060

通讯作者:

龙武剑（1977—），男，博士，教授。

作者简介:

冯甘霖（1989—），男，博士，副研究员。

Graphene Oxide-coated Sand for Enhancing Chloride Resistance of Cement-based Materials

Ganlin FENG¹^,²^,³, Shengyu LUO¹, Qiling LUO¹^,²^,³^,⁴, Wujian LONG¹^,²^,³^,⁴

Affiliations

^1.College of Civil and Transportation Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China

^2.Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, Shenzhen 518060, Guangdong, China

^3.Shenzhen Key Laboratory of Low Carbon Building Materials and Technology, Shenzhen 518060, Guangdong, China

^4.State Key Laboratory for Geomechanics & Deep Underground Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China

Corresponding Author:

LONG Wujian (1977-), male, Ph.D., Professor. E-mail: longwj@szu.edu.cn

FENG Ganlin (1989-), male, Ph.D., Associate researcher. E-mail: g-l.feng@szu.edu.cn

出版时间: 2025-03-20 doi: 10.14062/j.issn.0454-5648.20240579

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摘要

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氧化石墨烯（GO）的不均匀分散和团聚现象严重制约了其对水泥基复合材料孔隙结构及耐久性能的增强效果。通过将GO涂覆于氨基化砂粒表面，系统研究了其对GO水泥基复合材料抗氯离子侵蚀性能的影响规律及机理。结果显示：当GO掺量达到0.3%（质量分数）时，使用GO涂覆砂的方法，快速氯离子迁移测试氯离子渗透深度和扩散系数分别比对照组降低了24.8%和18.5%。压汞法测得有害孔级（>50 nm）孔径分布降低了36.8%。进一步的微观及物相分析测试结果表明，采用GO涂覆砂对水泥基复合材料性能提升的主要原因在于对界面过渡区的优化：一方面，氨丙基三乙氧基硅烷偶联剂通过与硅羧基的缩合反应紧密地连接到砂表面，另一方面，GO通过表面上的羰基或羧基和偶联剂氨基官能团之间的酰胺键共价键合，通过此“双键效应”GO可以稳定键合在砂表面从而改善其分散性，并同时促进界面过渡区水化，减少界面过渡区的缺陷和裂纹，从而大大提高水泥基复合材料对氯离子传输的抵抗能力。

关键词

氧化石墨烯涂覆砂 / 双重键合效应 / 抗氯离子侵蚀 / 界面过渡区

Abstract

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Introduction

In coastal engineering, the durability of reinforced concrete structures is often compromised due to the corrosion of steel reinforcements caused by chloride ingress. This issue significantly affects the safety and longevity of these structures. In concrete materials, the interfacial transition zone (ITZ) between the cement matrix and aggregates is a critical point, affecting the pathways and rates of chloride ion diffusion. Although previous studies demonstrate that the incorporation of nanomaterials can enhance the durability of cement-based materials, the uneven dispersion and agglomeration of these nanomaterials restrict their effectiveness. In this paper, a modification method was proposed via coating graphene oxide (GO) onto aminated sand particles to improve the dispersion of GO within cement-based composites, thereby enhancing their durability. This approach could have a promising potential for extending the service life of coastal engineering structures.

Methods

In this study, a GO dispersion was firstly prepared and dispersed by ultrasound. Subsequently, a specific chemical treatment method was employed to coat GO onto standard sand surfaces, creating aminated functionalized sand (GO-MAs). The preparation process of GO-MAs included sand pretreatment, amination, and chemical bonding with GO. In the experiments, cement-based composites with different GO contents (i.e., 0.1%, 0.3%, 0.5% by mass) were prepared with high-performance polycarboxylate superplasticizers to enhance GO dispersion. The chloride ion resistance of these composites was evaluated by rapid chloride migration (RCM) tests and natural chloride diffusion tests. In addition, the mechanisms of GO-coated sand enhancing the microstructural properties of cement-based materials, particularly the ITZ, were analyzed by mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and thermogravimetric analysis (TG/DTG).

Results and discussion

The experimental results indicate that the incorporation of GO significantly reduces the chloride ion penetration depth and migration coefficient in cement-based materials. At GO content of 0.3%, the chloride ion penetration depth and diffusion coefficient when using the method of using GO-coated sand can be reduced by 24.8% and 18.5%, respectively. The MIP tests further reveal that the size of harmful pores (i.e., greater than 50 nm) is decreased by 36.8%, indicating that GO-coated sand effectively improves the pore structure of cement-based materials, reduces porosity, and enhances material density. The microstructural analysis results reveal that GO-coated sand primarily enhances the performance of cement-based composites via optimizing the ITZ. The coupling agent forms stable chemical bonds with the sand surface, while the covalent bonding of amide bonds between GO and the coupling agent improves the dispersion of GO and promotes ITZ hydration, reducing defects and cracks, thereby enhancing resistance to chloride ion transport. The microstructural morphology analysis shows that the samples without GO have more and larger pores, while the samples with GO-coated sand exhibit significantly fewer and denser pores. The EDS analysis indicates that GO-coated sand promotes the enrichment of hydration products at the ITZ interface of cement-based materials, enhancing the ITZ density. Based on the XRD and TG/DTG analysis, GO-coated sand promotes the hydration reaction of cement, thus generating more hydration products, especially C-S-H and Ca(OH)₂ crystals. The formation and arrangement of these hydration products play a crucial role in maintaining a high alkaline environment within cement matrix and protecting a passivation film on the steel surface. The qualitative comparative analysis of the crystallographic orientation index of Ca(OH)₂ crystals indicates that GO-coated sand reduces the number of Ca(OH)₂ crystals perpendicular to the interface in the ITZ, optimizing the directional arrangement of Ca(OH)₂ crystals in the ITZ, which is beneficial for strengthening the weak interface and enhancing its density.

Conclusions

The method of using GO-coated sand effectively could enhance the resistance of cement-based materials to chloride ion erosion, and the optimal effect occurred at a GO content of 0.3%. This modification method optimized the ITZ through a "dual-bond effect," reducing porosity and increasing material density, thereby enhancing the barrier against chloride ions. This research could provide an effective technical approach to improving the durability of cement-based materials and offers important scientific evidence for the protection of concrete structures in coastal engineering. A future research needed to explore the long-term performance of GO-coated sand under different environmental conditions and its application effects in practical engineering, thus providing comprehensive theoretical support and technical guidance for the modification and engineering application of cement-based materials.

Key words

graphene oxide coated sand / double bond effect / anti chloride penetration / interfacial transition zone

引用本文

冯甘霖, 罗盛禹, 罗启灵, 龙武剑. 氧化石墨烯涂覆砂增强水泥基材料抗氯离子侵蚀性能. 硅酸盐学报, 2025 , 53 (3) : 505 -518 . DOI: 10.14062/j.issn.0454-5648.20240579

Ganlin FENG, Shengyu LUO, Qiling LUO, Wujian LONG. Graphene Oxide-coated Sand for Enhancing Chloride Resistance of Cement-based Materials[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (3) : 505 -518 . DOI: 10.14062/j.issn.0454-5648.20240579

基金

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国家自然科学基金资助项目(U2006223)

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2025年第53卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240579

接收时间：2024-09-03
首发时间：2026-10-22
出版时间：2025-03-20

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收稿日期：2024-09-03
修回日期：2024-09-25

基金

国家自然科学基金资助项目(U2006223)

作者信息

^1．深圳大学土木与交通工程学院，广东深圳 518060

^2．广东省滨海土木工程耐久性重点实验室，广东深圳 518060

^3．深圳市低碳建筑材料与技术重点实验室，广东深圳 518060

^4．深圳大学，深地工程智能建造与健康运维全国重点实验室，广东深圳 518060

通讯作者:

龙武剑（1977—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240579

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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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