硅酸盐学报

不同晶型碳酸钙对水泥浆体微观结构和性能演变的影响

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杨慧慧 ¹^,²^,³ , 张健 ¹^,²^,³ , 汪越 ¹^,²^,³ , 毛宇光 ¹^,²^,³ , 胡翔 ¹^,²^,³ , 史才军 ¹^,²^,³

硅酸盐学报 | 研究论文 2025,53(2): 349-366

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硅酸盐学报 |研究论文 2025 , 53 (2) : 349 -366

不同晶型碳酸钙对水泥浆体微观结构和性能演变的影响

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杨慧慧¹^,²^,³, 张健¹^,²^,³, 汪越¹^,²^,³, 毛宇光¹^,²^,³, 胡翔¹^,²^,³, 史才军¹^,²^,³

作者信息

^1．湖南大学，绿色先进土木工程材料及应用技术湖南省重点实验室，长沙 410082

^2．湖南大学，湖南省绿色与先进土木工程材料国际创新合作中心，长沙 410082

^3．湖南大学，建筑安全与节能教育部重点实验室，长沙 410082

通讯作者:

史才军（1963—），男，博士，教授。

作者简介:

杨慧慧（1999—），女，硕士研究生。

Influence of Different Calcium Carbonate Crystal on Microstructure and Performance Evolution of Cement Pastes

Huihui YANG¹^,²^,³, Jian ZHANG¹^,²^,³, Yue WANG¹^,²^,³, Yuguang MAO¹^,²^,³, Xiang HU¹^,²^,³, Caijun SHI¹^,²^,³

Affiliations

^1.Key Laboratory of Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, Hunan University, Changsha 410082, China

^2.International Innovation and Cooperation Center for Green & Advanced Civil Engineering Materials of Hunan Province, Hunan University, Changsha 410082, China

^3.Key Laboratory of Building Safety & Energy Conservation, Ministry of Education, Changsha 410082, China

Corresponding Author:

SHI Caijun (1963-), male, Ph.D., Professor. E-mail: cshi@hnu.edu.cn

YANG Huihui (1999-), female, Master candidate. E-mail: Yanghuihui@hnu.edu.cn

出版时间: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240208

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摘要

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研究了方解石和文石对水泥浆体微观结构和性能演变的作用机理。通过计算方解石和文石在水泥浆体中的填充效应、稀释效应、成核效应及化学效应，探究不同碳酸钙晶型对水泥浆体力学性能及微观结构演变的影响。结果表明：掺入适量的方解石或文石均可以促进水泥早期水化产物的生长和沉淀，水泥浆体早期抗压强度提高，此时碳酸钙的填充效应和成核效应发挥主要作用。水化7 d后，方解石或文石与铝相的反应程度提高，碳铝酸钙含量增多、水泥浆体孔隙率降低，化学效应的影响逐渐增加。文石相比于方解石，对于试件劈裂抗拉强度的提高主要与化学效应有关，反应产生的碳铝酸钙使文石与基体的粘结更加紧密。文石掺量20%~30%（质量分数），矿粉掺量5%~15%时，化学效应占比15%~21%，试件劈裂抗拉强度最多可提高39%。

关键词

碳酸钙 / 方解石 / 文石 / 水泥浆体 / 力学性能 / 微观结构

Abstract

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Introduction

The use of calcium carbonate powder as a mineral admixture in cementitious materials can reduce CO₂ emissions from clinker calcination and fossil fuel combustion, offering a low-carbon solution for sustainable cement production. Calcium carbonate can effectively fill the pores, refine the pore size, and promote the growth and precipitation of early hydration products of cement. On the other hand, calcium carbonate can react with the aluminum phase in cement to generate calcium carbon-aluminate, improving the mechanical properties of cementitious materials. There are two main crystal types of calcium carbonate in nature, calcite and aragonite. Due to the difference in density, stiffness and crystal structure of calcite and aragonite, calcite and aragonite-type calcium carbonate have different effects on the properties of cementitious materials. This paper elucidated the effects of different crystal types of calcium carbonate on the microstructure and mechanical properties of cement pastes and calculated the various effects of calcium carbonate in cement pastes, which would provide a solid and effective theoretical basis for the application of calcite and aragonite in engineering practice.

Methods

The raw materials used in this study include Portland cement (P·I 42.5), slag, calcite and aragonite. The calcite and aragonite were prepared by wet carbonation and analyzed for composition and purity by XRD and TG. Calcite and aragonite were separately added to the cement-slag composite system to prepare two groups of ternary systems with a water-cement ratio of 0.4. The simplex-centroid mixture design method was used to optimize the relative composition design of the raw materials in the cement pastes. According to the cement pastes composition design, 20 mm×20 mm×20 mm specimens were moulded for testing compressive strength, ϕ20 mm×40 mm specimens were moulded for testing splitting tensile strength, and ϕ25 mm×25 mm specimens were moulded for pore structure analysis.

The mechanical properties and pore structure of the specimens were tested after curing for 3, 7, 28 d and 90 d in standard curing conditions (temperature (20±1)℃, relative humidity ≥ 96%). The cement paste powders of corresponding age were taken for XRD and TG tests to analyse the type and content of hydration products. Finally, the nucleation effect, dilution effect, filling effect and chemical effect were quantified based on the contribution of calcite and aragonite to the sample compactness.

Results and discussion

The addition of approximately 15% calcite or aragonite enhanced the compressive strength of the cement paste during early hydration. This was because calcite or aragonite promoted cement hydration, improved the early hydration degree of cement, and increased the content of hydration products such as Ca(OH)₂ and C-S-H. The compressive strength of the calcite specimen was significantly higher than that of the aragonite specimen at the same dosage. Since the density of calcite was lower than that of aragonite, the filling effect of calcite was higher than that of aragonite, and calcite had a more significant nucleation effect than aragonite, with more hydration products deposited on the surface.

After 28 days of hydration, the compressive strength and splitting tensile strength of specimens mixed with calcium carbonate and slag were significantly increased. The synergistic effect of calcium carbonate and slag significantly improved the chemical reaction degree of calcium carbonate, and increased the content of calcium carboaluminate. Meanwhile, the formation of calcium carboaluminate inhibited the transformation of ettringite into calcium monosulfoaluminate, the solid phase volume of hydrated product increased, and the compactness of cement paste increased. Therefore, the mixture of slag and calcium carbonate was conducive to the continuous improvement of the mechanical properties of cement pastes.

With the increase of hydration age, the toughening effect of aragonite on cement paste was gradually improved. At 90 d of hydration, the content of aragonite was 20%~30% (in mass), the content of slag was 5%~15%, the contribution of chemical effect to the cement paste compactness was 15%~21%, and the splitting tensile strength of the specimen was increased by 39% compared with that of pure cement specimens. The improvement of the tensile strength of aragonite was mainly related to the chemical effect. The calcium carboaluminate formed by the reaction strengthened the bond between aragonite and cement paste, enhancing the toughening effect of aragonite.

Conclusions

The compressive strength of calcite specimens was found to be higher than that of aragonite specimens at the same calcium carbonate content during the early stage of hydration, primarily due to the increased filling and nucleation effects exhibited by calcite compared to aragonite. Due to the toughening effect of fibrous aragonite in cement pastes, the splitting tensile strength of the aragonite system was significantly higher than that of the calcite system. With the increase of hydration age, the reaction degree of calcium carbonate and aluminum phase in the composite system increased, the chemical effect continued to increase, and the compactness of the matrix increased. The addition of calcite or aragonite and slag was beneficial to the continuous improvement of the mechanical properties of the cement pastes. The increase in calcium carboaluminate content enhanced the toughening effect of aragonite and significantly increased the splitting tensile strength of the mixed specimens.

Key words

calcium carbonate / calcite / aragonite / cement paste / mechanical property / microstructure

引用本文

杨慧慧, 张健, 汪越, 毛宇光, 胡翔, 史才军. 不同晶型碳酸钙对水泥浆体微观结构和性能演变的影响. 硅酸盐学报, 2025 , 53 (2) : 349 -366 . DOI: 10.14062/j.issn.0454-5648.20240208

Huihui YANG, Jian ZHANG, Yue WANG, Yuguang MAO, Xiang HU, Caijun SHI. Influence of Different Calcium Carbonate Crystal on Microstructure and Performance Evolution of Cement Pastes[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (2) : 349 -366 . DOI: 10.14062/j.issn.0454-5648.20240208

基金

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国家自然科学基金(52078204)

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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.0454-5648.20240208

接收时间：2024-03-13
首发时间：2026-10-22
出版时间：2025-02-20

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收稿日期：2024-03-13
修回日期：2024-04-29

基金

国家自然科学基金(52078204)

作者信息

^1．湖南大学，绿色先进土木工程材料及应用技术湖南省重点实验室，长沙 410082

^2．湖南大学，湖南省绿色与先进土木工程材料国际创新合作中心，长沙 410082

^3．湖南大学，建筑安全与节能教育部重点实验室，长沙 410082

通讯作者:

史才军（1963—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240208

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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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