硅酸盐学报

镁/磷掺杂对高硫型高贝利特硫铝酸盐熟料烧成及性能的影响

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

硅酸盐学报 | 研究论文 2025,53(11): 3091-3100

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硅酸盐学报 |研究论文 2025 , 53 (11) : 3091 -3100

镁/磷掺杂对高硫型高贝利特硫铝酸盐熟料烧成及性能的影响

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

作者信息

^1．中国建筑材料科学研究总院有限公司，北京 100024

^2．天津城建大学材料科学与工程学院，天津 300384

通讯作者:

叶家元（1980—），男，博士，教授级高级工程师。

作者简介:

任雪红（1984—），女，博士，教授级高级工程师。

Effects of Magnesium and Phosphorus co-Doping on the Formation and Properties of Sulfate-Rich Belite Sulfoaluminate Clinker

Xuehong REN¹, Xiaoyue ZHAO¹^,², Jiayuan YE¹, Lei ZHANG², Wensheng ZHANG¹, Hongtao ZHANG¹, Lixue CAO¹

Affiliations

^1.China Building Materials Academy Co., Ltd., Beijing 100024, China

^2.School of Materials Science and Engineering, Tianjin Chengjian University, Tianjin 300384, China

Corresponding Author:

YE Jiayuan (1980-), male, Ph.D., Professor. E-mail: yejiayuan@cbma.com.cn

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

出版时间: 2025-11-20 doi: 10.14062/j.issn.0454-5648.20250382

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摘要

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镁和磷作为原料组分可显著调控高硫型高贝利特硫铝酸盐熟料的烧成行为与性能，但镁/磷的协同作用机制尚不明确。采用X射线衍射结合Rietveld方法、扫描电子显微镜等表征手段，研究了镁/磷复合掺杂对熟料矿物形成、微观结构及性能的影响及机理。结果表明：P⁵⁺选择性取代钙和铝/硅位点，促进稳定硅酸二钙（α'-C₂S）和硫铝酸钙（c-C₄A₃$）等活性晶型；而Mg²⁺与P⁵⁺竞争钙位点，不利于稳定活性晶型，当掺1%（质量分数，下同）MgO、1.3% P₂o₅时，α'-C₂S含量相对最高。适量镁/磷掺入促进C₂S矿物形成，当掺1.5% MgO、0.4% P₂O₅时，C₂S生成量最高，28 d强度达到74.5 MPa；过量MgO会引发方镁石形成，导致强度显著下降。

关键词

高硫型高贝利特硫铝酸盐水泥熟料 / 镁 / 磷 / α'-硅酸二钙 / 硫铝酸钙 / 强度

Abstract

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Introduction

The long-term strength development of high-sulfur belite-calcium sulfoaluminate (high-sulfur BCSA) cement remains constrained by the low hydration reactivity of β-dicalcium silicate (β-C₂S) and the difficulty in obtaining its high-temperature active polymorphs. Ionic doping, which activates and stabilizes highly cementitious dicalcium silicate/calcium sulfoaluminate (C₄A₃$) crystalline phases while inducing lattice distortion, has been proven as an effective approach to enhance mineral reactivity.

With the depletion of high-grade limestone resources, the utilization of low-grade magnesian limestone and phosphorus-containing solid wastes, such as phosphogypsum and phosphorus slag, for producing high-sulfur BCSA has become an inevitable trend. This leads to the unavoidable coexistence of Mg²⁺/P⁵⁺ in the clinker mineral system. However, existing studies have primarily focused on the doping effects of individual ions, while the synergistic influence and underlying mechanisms of magnesium/phosphorus components in the quaternary clinker system (C₂S-C₄A₃$-C₄AF-CaSO₄) on sintering behavior and performance remain poorly understood.

In this study, MgCO₃ and Ca₃(PO₄)₂ were employed as the sources of MgO and P₂O₅ doping, respectively, to systematically investigate the effects of Mg/P co-doping on the phase composition, crystal structure evolution, and mechanical properties of high-sulfur BCSA clinker, along with the associated mechanisms. The findings not only provide a theoretical foundation for optimizing the strength development of high-sulfur BCSA cement but also establish a technical basis for the large-scale, high-value utilization of Mg/P-bearing industrial solid wastes.

Methods

The designed mineral composition of high-sulfur BCSA clinker was as follows (mass fraction): 50 % C₂S, 30% C₄A₃$, 7% C₄AF, and 13% f-CaSO₄. The raw meal samples were prepared using industrial raw materials and analytical-grade chemical reagents with varying Mg/P doping levels. Specifically, MgO was incorporated at 0.6%, 1.0%, 1.5%, 3.0%, and 5.0%, while P₂O₅ was added at 0.1%, 0.4%, 0.7%, 1.0%, and 1.3%. The raw mixes were fired at 1320 ℃ for 60 min to obtain clinker samples.

The effects of Mg/P co-doping on the sintering behavior and properties of high-sulfur BCSA clinker were investigated through X-ray diffraction combined with Rietveld refinement, scanning electron microscopy, and mechanical strength testing.

Results and discussion

The Mg/P co-doping exhibits a significant synergistic effect, with an appropriate doping ratio effectively enhancing the content of highly reactive mineral phases, including cubic-calcium sulfoaluminate (c-C₄A₃$) and α'-dicalcium silicate (α'-C₂S). P₂O₅ demonstrates a favorable stabilizing effect on high-activity crystalline phases such as α'-C₂S and c-C₄A₃$, whereas MgO shows an adverse influence, particularly when the P₂O₅ content is low (P₂O₅ ≤ 0.4%). The maximum α'-C₂S formation in clinker is achieved at a doping level of 1% MgO and 1.3% P₂O₅. Moreover, Mg/P co-doping reduces the grain size of C₂S and C₄A₃$ minerals. However, excessive P₂O₅ doping 1.3% leads to noticeable melting corrosion, resulting in decreased crystallinity.

At low doping levels [w(MgO) ≤ 1.5%, w(P₂O₅) ≤ 0.7%], the 3 d compressive strength improves while the 7 d strength remains stable, with all samples showing varying degrees of enhancement in 28 d compressive strength, though excessive MgO doping leads to periclase formation and significant strength reduction. The 3 d and 28 d compressive strengths exhibit linear correlations with the total contents of C₄A₃$ and C₂S, respectively, with appropriate Mg/P doping promoting C₂S formation, particularly at 1.5% MgO and 0.4% P₂O₅, which yields the highest C₂S content and achieves a 28 d strength of 74.5 MPa.

Conclusions

Optimal Mg/P co-doping effectively reduces the decomposition temperature of CaCO₃ while enhancing its decomposition rate, and lowers the formation temperature of intermediate minerals C₅S₂$ and C₂S within the 900-1320 ℃ range, thereby promoting the formation of clinker minerals like C₂S. Furthermore, Mg/P doping demonstrates significant synergistic effects: P⁵⁺ selectively substitutes calcium and aluminum/silicon sites, stabilizing reactive phases such as α'-C₂S and c-C₄A₃$. As P₂O₅ content increases from 0.4% to 1.3%, the concentrations of α'-C₂S and c-C₄A₃$ markedly rise. In contrast, Mg²⁺ competes with P⁵⁺ for calcium sites, leading to reduced α'-C₂S and c-C₄A₃$ content with increasing MgO doping. The highest relative α'-C₂S content (51.5%) is achieved at 1% MgO and 1.3% P₂O₅ doping levels.

The 28 d compressive strength of doped clinker was improvd to varying degrees, initially increasing with MgO content but declining when excessive MgO forms periclase. Similarly, strength first rises then falls with increasing P₂O₅ content. Both 3 d and 28 d compressive strengths exhibit linear positive correlations with the total contents of C₄A₃$ and C₂S, respectively. Maximum C₂S formation and peak 28 d strength (74.5 MPa) occur at 1.5% MgO and 0.4% P₂O₅ doping. Comprehensive analysis of mineral formation, crystal phases, and performance reveals an optimal doping range: w(MgO)<3% and w(P₂O₅) 0.3%-1.3%, which balances clinker sintering efficiency and mechanical properties.

Key words

high-sulfur belite-calcium sulfoaluminat cement clinker / magnesium / phosphorus / α'-dicalcium silicate / calcium sulfoaluminate / strength

引用本文

任雪红, 赵晓悦, 叶家元, 张磊, 张文生, 张洪滔, 曹立学. 镁/磷掺杂对高硫型高贝利特硫铝酸盐熟料烧成及性能的影响. 硅酸盐学报, 2025 , 53 (11) : 3091 -3100 . DOI: 10.14062/j.issn.0454-5648.20250382

Xuehong REN, Xiaoyue ZHAO, Jiayuan YE, Lei ZHANG, Wensheng ZHANG, Hongtao ZHANG, Lixue CAO. Effects of Magnesium and Phosphorus co-Doping on the Formation and Properties of Sulfate-Rich Belite Sulfoaluminate Clinker[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (11) : 3091 -3100 . DOI: 10.14062/j.issn.0454-5648.20250382

基金

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国家自然科学基金专项(52341202)

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2025年第53卷第11期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250382

接收时间：2025-05-14
首发时间：2026-10-21
出版时间：2025-11-20

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收稿日期：2025-05-14
修回日期：2025-06-13

基金

国家自然科学基金专项(52341202)

作者信息

^1．中国建筑材料科学研究总院有限公司，北京 100024

^2．天津城建大学材料科学与工程学院，天津 300384

通讯作者:

叶家元（1980—），男，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.0454-5648.20250382

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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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