硅酸盐学报

晶种对硫铝改性低钙硅酸盐水泥熟料烧成的影响及机理

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赵晓悦 ¹^,² , 任雪红 ² , 张磊 ¹ , 张文生 ² , 叶家元 ² , 张洪滔 ² , 曹立学 ² , 陈绍良 ²

硅酸盐学报 | 研究论文 2025,53(1): 37-46

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硅酸盐学报 |研究论文 2025 , 53 (1) : 37 -46

晶种对硫铝改性低钙硅酸盐水泥熟料烧成的影响及机理

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赵晓悦¹^,², 任雪红², 张磊¹, 张文生², 叶家元², 张洪滔², 曹立学², 陈绍良²

作者信息

^1．天津城建大学材料科学与工程学院，天津 300384

^2．中国建筑材料科学研究总院有限公司，绿色建筑材料国家重点实验室，北京 100024

通讯作者:

任雪红（1984—），女，博士，教授级高级工程师。

作者简介:

赵晓悦（1999—），女，硕士研究生。

Influences of Crystal Seed on Formation of Calcium Sulfoaluminate Modified Low-Calcium Portland Cement Clinker

Xiaoyue ZHAO¹^,², Xuehong REN², Lei ZHANG¹, Wensheng ZHANG², Jiayuan YE², Hongtao ZHANG², Lixue CAO², Shaoliang CHEN²

Affiliations

^1.School of Materials Science and Engineering, Tianjin Chengjian University, Tianjin 300384, China

^2.State Key Laboratory of Green Building Materials, China Building Materials Academy Co., Ltd., Beijing 100024, China

Corresponding Author:

REN Xuehong (1984-), female, Ph.D., Professor. E-mail: renxue968@163.com

ZHAO Xiaoyue (1999-), female, Master candidate. E-mail: zhao_xyue@163.com

出版时间: 2025-01-20 doi: 10.14062/j.issn.0454-5648.20240360

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摘要

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为了设计发展新型低钙水泥熟料，采用原位高温X射线衍射、扫描电子显微镜及热分析等，以硅酸盐水泥熟料中硅酸三钙（C₃S）、硅酸二钙（C₂S）等矿物为晶种，研究了硅酸盐水泥熟料添加对硫铝改性低钙硅酸盐水泥熟料的形成、矿物组成和微观结构等的影响及其机理。结果表明：硅酸盐水泥熟料的掺入促进了液相烧结，C₂S和硫铝酸钙（C₄A₃$）晶粒尺寸增大。在熟料晶种中C₂S和铁相的诱导作用下，C₂S和铁相的含量增加；由于熟料晶种中C₃S在低温分解，未能起到促进C₃S形成及其与C₄A₃$共存的作用，且当硅酸盐水泥熟料掺量为10%（质量分数）时，C₄A₃$含量明显降低。此外，由于化学成分固溶变化，熟料晶种促进稳定β-C₂S和o-C₄A₃$，但不利于高活性晶型矿物α′-C₂S和c-C₄A₃$的稳定。

关键词

晶种 / 低钙硅酸盐水泥熟料 / 硫铝酸钙 / 硅酸二钙 / 硅酸三钙 / 液相

Abstract

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Introduction

The existing cement clinker systems have some challenges. The production process of calcium sulfoaluminate (CSA) clinker, which primarily contains mineral C₄A₃$, requires a significant amount of high-quality bauxite resources, thus leading to a higher production cost. Compared to CSA, a high belite calcium sulfoaluminate (BCSA) cement reduces the demand for high-grade bauxite during production, but has a slower strength development over time. To ensure the synergistic development of both early age performance and strength development in clinker systems, calcium sulfoaluminate-modified Portland cement (designated as S.M.P.) is further developed. However, alite (C₃S) remains a dominant mineral, resulting in relatively high carbon emissions.

For the compositional and performance characteristics of S.M.P. and BCSA clinker, this study proposed a new system for preparing a low-calcium calcium sulfoaluminate-modified Portland cement clinker with belite (C₂S) as a dominant mineral (i.e., C₃S/C₂S-C₄A₃S-C₄AF-CaSO₄).

This study also utilized minerals such as C₃S and C₂S from Portland cement clinker as crystal seed additives. The effect of adding Portland cement clinker on the sintering process and the mineral composition structure of the low-calcium calcium sulfoaluminate-modified Portland cement clinker was investigated. In addition, the underlying mechanisms were explored to provide a theoretical and technical guidance for the design and development of low-calcium cement clinkers.

Methods

The designed mineral composition of the calcium sulfoaluminate-modified low-calcium Portland cement clinker was 45%-50% (in mass, the same below) of C₂S, 5%-10% of C₃S, 25% of C₄A₃$, 10% of C₄AF, and 10% of f-CaSO₄. Calcium sulfoaluminate-modified low-calcium Portland raw meals were prepared with industrial raw materials. Portland cement clinker was used as a crystal seed at different incorporation contents of 0%, 1%, 3%, 5%, 10%, and 12%.

The mineral composition and microstructure of calcium sulfoaluminate-modified low-calcium Portland cement clinker were determined by in-situ high-temperature X-ray diffraction (XRD), linear shrinkage measurement, free lime titration, scanning electron microscopy (SEM) and thermal analysis.

Results and Discussion

The linear shrinkage of the samples generally increases gradually with the increase in clinker addition percentage from 0% to 10%. The linear shrinkage remains relatively unchanged at >12% of clinker additions. The XRD patterns of the synthesized clinker samples within the 20° to 51° range reveal that the diffraction peak intensity of β-C₂S gradually increases, while the intensity of α′-C₂S and C₄A₃$ peaks decreases, and no significant diffraction peaks for C₃S appear as the clinker crystal seed content increases.

The analysis by rietveld whole-pattern fitting indicates that the addition of Portland cement clinker seeds does not lead to a significant increase in C₃S content. There is a notable increase in C₂S content and a gradual decrease in C₄A₃$ content, accompanied by a relative increase in the iron phase content.

The high-temperature in-situ XRD patterns indicate that at 950 ℃, an original C₃S diffraction peak disappears, instead of relatively weak C₂S diffraction peaks at approximately 27.5° and 38.0°. This indicates that C₃S decomposes into C₂S and CaO at 950 ℃.

According to the analysis by backscattered electron-energy dispersive spectroscopy (BSE-EDS), the solid solubility of aluminum, sulfur and iron in C₂S increases with increasing the addition of clinker crystal seeds, thus favoring the stability of β-C₂S. Furthermore, the presence of sulfur impedes a reaction between C₂S and CaO, thus inhibiting the formation of C₃S. An increase in the iron phase content and the Al/Fe ratio within this phase, coupled with enhanced Al solubility in C₂S, reduces the amount of Al available for sulfate reaction.

Conclusions

The incorporation of Portand cement clinker seeds facilitated the formation of liquid phases, favoring the liquid-phase sintering of clinker and enhancing the densification of the microstructure of the synthesized clinker samples. This incorporation also increased the grain sizes of C₂S and C₄A₃$. The introduction of clinker seeds lowered the decomposition temperature of CaCO₃, promoting the formation of C₂S and C₄AF. Consequently, the contents of C₂S and the iron phase increased sulfur-aluminous modified low-calcium Portand cement clinker. However, the decomposition of C₃S in clinker crystal seeds at lower temperatures prevented an effective promotion of C₃S formation alongside C₄A₃$.

The content of the iron phase and the Al/Fe ratio increased with increasing the addition of clinker crystal seeds. Increased Al solubility in C₂S led to a reduction in the Al available for sulfate reactions, thereby decreasing the formation of C₄A₃$. This effect was particularly pronounced when the clinker crystal seed content reached 10%, resulting in a significant reduction in C₄A₃$ content.

The inclusion of Portland cement clinker seeds led to a decrease in the content of highly reactive α′-C₂S and c-C₄A₃$ in the clinker. As the clinker crystal seed content increased, this reduction becomes dominant. This was primarily due to an increase in the calcium-to-silicon ratio in C₂S and an increased dissolution of Al, Fe, and S in C₂S, stabilizing β-C₂S but destabilizing α′-C₂S, and was not conducive to C₃S formation. Concurrently, a decreased Fe dissolution in C₄A₃$ favored the stabilization of orthorhombic C₄A₃$ rather than cubic C₄A₃$.

Key words

crystal seed / low-calcium portland cement clinker / calcium sulfoaluminate / dicalcium silicate / tricalcium silicate / liquid phase

引用本文

赵晓悦, 任雪红, 张磊, 张文生, 叶家元, 张洪滔, 曹立学, 陈绍良. 晶种对硫铝改性低钙硅酸盐水泥熟料烧成的影响及机理. 硅酸盐学报, 2025 , 53 (1) : 37 -46 . DOI: 10.14062/j.issn.0454-5648.20240360

Xiaoyue ZHAO, Xuehong REN, Lei ZHANG, Wensheng ZHANG, Jiayuan YE, Hongtao ZHANG, Lixue CAO, Shaoliang CHEN. Influences of Crystal Seed on Formation of Calcium Sulfoaluminate Modified Low-Calcium Portland Cement Clinker[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (1) : 37 -46 . DOI: 10.14062/j.issn.0454-5648.20240360

基金

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国家自然科学基金项目(52341202)
中国建材集团攻关专项(2021HX0304)

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2025年第53卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240360

接收时间：2024-05-23
首发时间：2026-10-22
出版时间：2025-01-20

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出版历史

收稿日期：2024-05-23
修回日期：2024-06-27

基金

国家自然科学基金项目(52341202)

中国建材集团攻关专项(2021HX0304)

作者信息

^1．天津城建大学材料科学与工程学院，天津 300384

^2．中国建筑材料科学研究总院有限公司，绿色建筑材料国家重点实验室，北京 100024

通讯作者:

任雪红（1984—），女，博士，教授级高级工程师。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240360

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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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