Article(id=1308544303287329345, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1308544285121798644, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250244, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1743436800000, receivedDateStr=2025-04-01, revisedDate=1744732800000, revisedDateStr=2025-04-16, acceptedDate=null, acceptedDateStr=null, onlineDate=1789910873481, onlineDateStr=2026-09-20, pubDate=1754582400000, pubDateStr=2025-08-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1789910873481, onlineIssueDateStr=2026-09-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1789910873481, creator=13701087609, updateTime=1789910873481, updator=13701087609, issue=Issue{id=1308544285121798644, tenantId=1146029695717560320, journalId=1263187385517883426, year='2026', volume='54', issue='5', pageStart='1499', pageEnd='1880', issueExtLink='null', onlineDate='null', pubDate='1779206400000', pubDateStr='2026-05-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1789910869150, creator='13701087609', updateTime=1789955421627, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1308731151825600702, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1308544285121798644, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1308731151825600703, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1308544285121798644, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1545, endPage=1554, ext={EN=ArticleExt(id=1308544303497044546, articleId=1308544303287329345, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=M-value Effect on Properties of Sulphosilicate Cement and Its Hydration Mechanism, columnId=1308544284861759516, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on Low-Carbon Cement and Solid Waste Resource Utilization—Research Articles, runingTitle=null, highlight=null, articleAbstract=
Introduction

The sulfate source in calcium sulfoaluminate (CSA) cement is an important factor that determines its hydration characteristics, and the properties of CSA cement can be controlled via adjusting the molar ratio of calcium sulfate to ye'elimite (generally referred to as the "M-value"). Sulphosilicate cement is a novel cementitious material developed via incorporating ternesite (C5S2$) and free-calcium sulfate (f-C$) into the mineral composition of CSA cement. The calculation of the M-value must comprehensively account for their contents in the clinker due to the presence of SO3 in C5S2$ and f-C$. This study optimized the conventional calculation formula for the M-value and systematically investigated its influence on the compressive strength and expansion behavior of sulphosilicate cement. In addition, the mechanism underlying the effect of anhydrite dosage on cement hydration was also elucidated through the evolution of hydration products.

Methods

In this experiment, sulphosilicate clinker was synthesized with limestone, fly ash, phosphogypsum, and bauxite as raw materials. The raw materials were calcined at 1250 ℃ for 1 h, followed by rapid air quenching to obtain the clinker. Five groups of sulphosilicate cement with M-values of 0, 0.9, 1.8, 2.7, and 3.6 were designed. Mortar specimens were prepared to evaluate compressive strength and expansion rate, while paste specimens were prepared for analyzing hydration product characteristics at specific ages. The hydration heat release was measured by an isothermal calorimeter. The phase compositions and microstructure of the hydration products were analyzed by X-ray diffractometer, thermal behavior analyzer and field-emission environmental scanning electron microscope. The pore structure was performed by a mercury intrusion porosimeter.

Results and discussion

Among the various sulphoaluminate cement groups, the M1.8 specimen demonstrates the maximum compressive strength of 43.9 MPa after 3-d hydration. As hydration progresses, the compressive strength of the M2.7 and M3.6 groups shows a significant growth, with the M3.6 group reaching 56.7 MPa at 14 d. However, the M3.6 specimen exhibits a notable strength retrogression, which, is decreased by 4.3 MPa, after 28-d hydration. In contrast, the compressive strength of the M0.9 group increases markedly from 14 d to 28 d, with an improvement of 12.3 MPa.

For specimens with the M-value below 1, the early hydration products at 3 d are dominated by AFm phases with insufficient AFt content, resulting in an initial shrinkage. As hydration progresses, the dissolution of SO3 from anhydrite and C5S2$ promotes AFt formation, leading to a measurable expansion after 7 d. At low M-values, AFt contributes to pore refinement, while the reaction of C5S2$ and C2S in later stages generates C-(A)-S-H gel and stratlingite (C2ASH8), refining the microstructure of hydration products and enhancing long-term strength. In contrast, specimens with higher M-values (i.e., 1.8, 2.7, and 3.6) exhibit expansion as early as 3 d. Increased anhydrite content and prolonged hydration amplify the crystallographic stress exerted by AFt crystals on the surrounding matrix, causing coarsening of pores, and elevated total porosity, and resulting in strength retrogression during 14-28 d of curing.

Conclusions

This study was to propose a formula for calculating the gypsum coefficient M-value in sulphosilicate cement, i.e., CG= 0.13 × M × (Y - A×2.24 - T×1.27)/Sg, establishing the relationship between gypsum dosage and cement performance, while elucidating the influence of M-values on the mechanical properties and hydration mechanisms. The experimental results demonstrated that within the optimal M-range of 0.9-1.8, cement could achieve continuous strength development for all curing ages. Higher M-values (2.7-3.6) enhanced mid-term strength but induced strength regression at 28 d. Increasing M-values effectively suppressed early-age shrinkage and induced progressive expansion, and expansion rates were positively correlated to M-values at all hydration stages. Hydration products primarily consisted of AFt, AH3, and C-(A)-S-H gel. At M0 and M0.9, AFm phases formed during early hydration, followed by C2ASH8 in later stages. Conversely, M-values of ≥1.8 accelerated C4A3$ hydration but inhibited both C5S2$ dissolution and C2ASH8 formation. Microstructurally, M0.9 specimens exhibited pore refinement and reduced porosity through gel-phase densification, enhancing strength development, whereas M3.6 samples suffered from coarse pore proliferation due to excessive anhydrite content promoting oversized AFt crystals, ultimately degrading 28-d strength. At the M-value of 0.9-1.8, the system achieved balanced high strength and minimal volumetric deformation, making it suitable for general engineering applications. Elevating the M-value to 1.8-2.7 induced a controlled expansion behavior, enabling targeted use in shrinkage compensation scenarios. However, at the M value of 3.6, delayed strength retrogression and microstructural deterioration could occur, thus establishing 3.6 as a critical upper limit for M-values.

, authors=Lixue CAO, Xuehong REN, Jiayuan YE, Yanze WU, Dong DONG, Shaoliang CHEN, Wensheng ZHANG, authorsList=Lixue CAO, Xuehong REN, Jiayuan YE, Yanze WU, Dong DONG, Shaoliang CHEN, Wensheng ZHANG, authorCompany=null, correspAuthors=Xuehong REN, authorNote=

CAO Lixue (1994-), male, Doctoral candidate. E-mail:

, correspAuthorsNote=
REN Xuehong (1984-), female, Ph. D., Professor. E-mail:
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硫硅酸盐水泥是在硫铝酸盐水泥体系基础上提出的新型低碳水泥,石膏掺量是影响硫硅酸盐水泥性能发展的重要因素,本工作提出了石膏系数(M值)确定石膏掺量的公式,系统研究了M值对硫硅酸盐水泥抗压强度、膨胀率、水化放热和水化产物组成及结构的影响。结果表明:M值增加提高了硫硅酸盐水泥早期抗压强度,降低了水泥的早期收缩,并诱导产生中后期膨胀;当M值达到3.6时,水泥水化28 d后,硬化浆体中有害孔增多,抗压强度出现倒缩。M值为0、0.9时,硫硅酸钙和硅酸二钙在水化后期能反应生成C-(A)-S-H凝胶和水化硅铝酸钙(C2ASH8);M值为1.8、2.7、3.6时,促进了硫铝酸钙水化和钙矾石晶体的生长发育,抑制了硫硅酸钙和硅酸二钙的水化。本工作提出了硫硅酸盐水泥的M值并据此确定了该水泥性能与石膏掺量的关系,为充分发挥硫硅酸盐水泥性能奠定了基础,为推进硫硅酸盐水泥工程应用提供了理论依据。

, authors=曹立学, 任雪红, 叶家元, 武岩泽, 董栋, 陈绍良, 张文生, authorsList=曹立学, 任雪红, 叶家元, 武岩泽, 董栋, 陈绍良, 张文生, authorCompany=null, correspAuthors=任雪红, authorNote=

曹立学(1994—),男,博士研究生。

, correspAuthorsNote=
任雪红(1984—),女,博士,教授级高级工程师。
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M值对硫硅酸盐水泥性能的影响及水化机理
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曹立学 , 任雪红 , 叶家元 , 武岩泽 , 董栋 , 陈绍良 , 张文生
硅酸盐学报 | 低碳水泥与固废资源化利用专题—研究论文 2026,54(5): 1545-1554
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硅酸盐学报 |低碳水泥与固废资源化利用专题—研究论文 2026 , 54 (5) : 1545 -1554
M值对硫硅酸盐水泥性能的影响及水化机理
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曹立学(1994—),男,博士研究生。

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曹立学 , 任雪红 , 叶家元, 武岩泽, 董栋, 陈绍良, 张文生
作者信息
  • 中国建筑材料科学研究总院有限公司,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:

曹立学(1994—),男,博士研究生。

M-value Effect on Properties of Sulphosilicate Cement and Its Hydration Mechanism
Lixue CAO , Xuehong REN , Jiayuan YE, Yanze WU, Dong DONG, Shaoliang CHEN, Wensheng ZHANG
Affiliations
  • China Building Materials Academy, Beijing 100024, China
  • Corresponding Author:
    REN Xuehong (1984-), female, Ph. D., Professor. E-mail:

    CAO Lixue (1994-), male, Doctoral candidate. E-mail:

出版时间: 2025-08-08 doi: 10.14062/j.issn.0454-5648.20250244
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硫硅酸盐水泥是在硫铝酸盐水泥体系基础上提出的新型低碳水泥,石膏掺量是影响硫硅酸盐水泥性能发展的重要因素,本工作提出了石膏系数(M值)确定石膏掺量的公式,系统研究了M值对硫硅酸盐水泥抗压强度、膨胀率、水化放热和水化产物组成及结构的影响。结果表明:M值增加提高了硫硅酸盐水泥早期抗压强度,降低了水泥的早期收缩,并诱导产生中后期膨胀;当M值达到3.6时,水泥水化28 d后,硬化浆体中有害孔增多,抗压强度出现倒缩。M值为0、0.9时,硫硅酸钙和硅酸二钙在水化后期能反应生成C-(A)-S-H凝胶和水化硅铝酸钙(C2ASH8);M值为1.8、2.7、3.6时,促进了硫铝酸钙水化和钙矾石晶体的生长发育,抑制了硫硅酸钙和硅酸二钙的水化。本工作提出了硫硅酸盐水泥的M值并据此确定了该水泥性能与石膏掺量的关系,为充分发挥硫硅酸盐水泥性能奠定了基础,为推进硫硅酸盐水泥工程应用提供了理论依据。

M值  /  硫硅酸盐水泥  /  硬石膏  /  性能  /  水化机理
Introduction

The sulfate source in calcium sulfoaluminate (CSA) cement is an important factor that determines its hydration characteristics, and the properties of CSA cement can be controlled via adjusting the molar ratio of calcium sulfate to ye'elimite (generally referred to as the "M-value"). Sulphosilicate cement is a novel cementitious material developed via incorporating ternesite (C5S2$) and free-calcium sulfate (f-C$) into the mineral composition of CSA cement. The calculation of the M-value must comprehensively account for their contents in the clinker due to the presence of SO3 in C5S2$ and f-C$. This study optimized the conventional calculation formula for the M-value and systematically investigated its influence on the compressive strength and expansion behavior of sulphosilicate cement. In addition, the mechanism underlying the effect of anhydrite dosage on cement hydration was also elucidated through the evolution of hydration products.

Methods

In this experiment, sulphosilicate clinker was synthesized with limestone, fly ash, phosphogypsum, and bauxite as raw materials. The raw materials were calcined at 1250 ℃ for 1 h, followed by rapid air quenching to obtain the clinker. Five groups of sulphosilicate cement with M-values of 0, 0.9, 1.8, 2.7, and 3.6 were designed. Mortar specimens were prepared to evaluate compressive strength and expansion rate, while paste specimens were prepared for analyzing hydration product characteristics at specific ages. The hydration heat release was measured by an isothermal calorimeter. The phase compositions and microstructure of the hydration products were analyzed by X-ray diffractometer, thermal behavior analyzer and field-emission environmental scanning electron microscope. The pore structure was performed by a mercury intrusion porosimeter.

Results and discussion

Among the various sulphoaluminate cement groups, the M1.8 specimen demonstrates the maximum compressive strength of 43.9 MPa after 3-d hydration. As hydration progresses, the compressive strength of the M2.7 and M3.6 groups shows a significant growth, with the M3.6 group reaching 56.7 MPa at 14 d. However, the M3.6 specimen exhibits a notable strength retrogression, which, is decreased by 4.3 MPa, after 28-d hydration. In contrast, the compressive strength of the M0.9 group increases markedly from 14 d to 28 d, with an improvement of 12.3 MPa.

For specimens with the M-value below 1, the early hydration products at 3 d are dominated by AFm phases with insufficient AFt content, resulting in an initial shrinkage. As hydration progresses, the dissolution of SO3 from anhydrite and C5S2$ promotes AFt formation, leading to a measurable expansion after 7 d. At low M-values, AFt contributes to pore refinement, while the reaction of C5S2$ and C2S in later stages generates C-(A)-S-H gel and stratlingite (C2ASH8), refining the microstructure of hydration products and enhancing long-term strength. In contrast, specimens with higher M-values (i.e., 1.8, 2.7, and 3.6) exhibit expansion as early as 3 d. Increased anhydrite content and prolonged hydration amplify the crystallographic stress exerted by AFt crystals on the surrounding matrix, causing coarsening of pores, and elevated total porosity, and resulting in strength retrogression during 14-28 d of curing.

Conclusions

This study was to propose a formula for calculating the gypsum coefficient M-value in sulphosilicate cement, i.e., CG= 0.13 × M × (Y - A×2.24 - T×1.27)/Sg, establishing the relationship between gypsum dosage and cement performance, while elucidating the influence of M-values on the mechanical properties and hydration mechanisms. The experimental results demonstrated that within the optimal M-range of 0.9-1.8, cement could achieve continuous strength development for all curing ages. Higher M-values (2.7-3.6) enhanced mid-term strength but induced strength regression at 28 d. Increasing M-values effectively suppressed early-age shrinkage and induced progressive expansion, and expansion rates were positively correlated to M-values at all hydration stages. Hydration products primarily consisted of AFt, AH3, and C-(A)-S-H gel. At M0 and M0.9, AFm phases formed during early hydration, followed by C2ASH8 in later stages. Conversely, M-values of ≥1.8 accelerated C4A3$ hydration but inhibited both C5S2$ dissolution and C2ASH8 formation. Microstructurally, M0.9 specimens exhibited pore refinement and reduced porosity through gel-phase densification, enhancing strength development, whereas M3.6 samples suffered from coarse pore proliferation due to excessive anhydrite content promoting oversized AFt crystals, ultimately degrading 28-d strength. At the M-value of 0.9-1.8, the system achieved balanced high strength and minimal volumetric deformation, making it suitable for general engineering applications. Elevating the M-value to 1.8-2.7 induced a controlled expansion behavior, enabling targeted use in shrinkage compensation scenarios. However, at the M value of 3.6, delayed strength retrogression and microstructural deterioration could occur, thus establishing 3.6 as a critical upper limit for M-values.

M-value  /  sulphosilicate cement  /  anhydrite  /  properties  /  hydration mechanism
曹立学, 任雪红, 叶家元, 武岩泽, 董栋, 陈绍良, 张文生. M值对硫硅酸盐水泥性能的影响及水化机理. 硅酸盐学报, 2026 , 54 (5) : 1545 -1554 . DOI: 10.14062/j.issn.0454-5648.20250244
Lixue CAO, Xuehong REN, Jiayuan YE, Yanze WU, Dong DONG, Shaoliang CHEN, Wensheng ZHANG. M-value Effect on Properties of Sulphosilicate Cement and Its Hydration Mechanism[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (5) : 1545 -1554 . DOI: 10.14062/j.issn.0454-5648.20250244
  • “十四五”国家重点研发计划(2022YFC3803101)
  • 国家自然科学基金“双碳”专项项目(52341202)
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doi: 10.14062/j.issn.0454-5648.20250244
  • 接收时间:2025-04-01
  • 首发时间:2026-09-20
  • 出版时间:2025-08-08
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  • 收稿日期:2025-04-01
  • 修回日期:2025-04-16
基金
“十四五”国家重点研发计划(2022YFC3803101)
国家自然科学基金“双碳”专项项目(52341202)
作者信息
    中国建筑材料科学研究总院有限公司,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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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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