硅酸盐学报

镁质胶凝材料相组成演化的热力学模拟研究进展

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李童 , 郭培洋 , 刘昌浩 , 陈惠苏

硅酸盐学报 | 第二十八届中国科协年会智能建造关键无机非金属材料–AI驱动水泥基材料创新专题-综合评述 2026,54(10): 3530-3551

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硅酸盐学报 |第二十八届中国科协年会智能建造关键无机非金属材料–AI驱动水泥基材料创新专题-综合评述 2026 , 54 (10) : 3530 -3551

镁质胶凝材料相组成演化的热力学模拟研究进展

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李童, 郭培洋, 刘昌浩, 陈惠苏

作者信息

东南大学材料科学与工程学院，重大基础设施工程材料全国重点实验室，南京　211189

通讯作者:

陈惠苏（1973-），男，博士，教授。

作者简介:

李童（1995-），男，博士研究生。

Thermodynamic Modeling of Phase Assemblage Evolution in Magnesia Cements: A Review

Tong LI, Peiyang GUO, Changhao LIU, Huisu CHEN

Affiliations

State Key Laboratory of Engineering Materials for Major Infrastructure, School of Materials Science and Engineering, Southeast University, Nanjing 211189, China

Corresponding Author:

CHEN Huisu (1973-), male, Ph.D., Professor. E-mail: chenhs@seu.edu.cn

LI Tong (1995-), male, Doctoral candidate. E-mail: 230228627@seu.edu.cn

出版时间: 2026-09-02 doi: 10.14062/j.issn.0454-5648.20260326

文章导航

摘要

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热力学模拟是研究镁质胶凝材料水化反应、物相演化和耐久性能的重要方法。本文从热力学模拟的基本原理出发，介绍了镁质胶凝材料常用活度系数模型、模拟软件及热力学数据库，系统总结了热力学模拟在水化硅酸镁水泥、磷酸镁水泥、硫氧镁水泥、氯氧镁水泥和活性氧化镁水泥等体系中的应用进展，重点分析和总结了配合比、改性剂和侵蚀性介质对水化产物组成及相稳定性的影响规律。现有研究表明，热力学模拟能够有效揭示镁质胶凝材料中含镁水化产物的形成与转化机制，为配合比优化设计和耐久性评价提供理论依据。然而，关键水化产物热力学数据不足和无定形凝胶相难以准确描述限制了热力学模拟的准确性。未来应进一步完善镁质胶凝材料热力学数据库，并建立“相组成-微结构-宏观力学性能”多尺度关联框架，为镁质胶凝材料的优化设计和工程应用提供支撑。

关键词

镁质胶凝材料 / 相组成 / 热力学模拟 / 热力学数据库

Abstract

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Magnesia cements have attracted increasing attention as low-carbon and functional binders because of their diverse reaction pathways, rapid hardening characteristics, and potential applications in rapid repair, fire-resistant boards, waste immobilization, carbon sequestration, and specialized engineering environments. Typical magnesia cement systems include magnesium silicate hydrate cement (M-S-H), magnesium phosphate cement (MPC), magnesium oxysulfate cement (MOS), magnesium oxychloride cement (MOC), and reactive magnesia cement (RMC). These systems involve complex reactions among MgO, soluble salts, siliceous or aluminosilicate components, water, and CO₂, leading to the formation of various hydration and carbonation products, such as M-S-H/M-(A)-S-H gels, 3Mg(OH)₂·MgCl₂·8H₂O, 5Mg(OH)₂·MgCl₂·8H₂O, 3Mg(OH)₂·MgSO₄·8H₂O, 5Mg(OH)₂·MgSO₄·7H₂O, and KMgPO₄·6H₂O. Because these products are often highly sensitive to mix proportion, temperature, pore solution chemistry, relative humidity, CO₂ concentration, and aggressive ions, it remains difficult to fully elucidate their phase assemblage evolution and long-term durability using experimental characterization alone. Thermodynamic modeling provides an effective approach to predict stable phase assemblages, pore solution composition, saturation indices, and phase stability boundaries under defined boundary conditions and has thus become an important tool for understanding the hydration, modification, degradation, and carbonation mechanisms of magnesia cements.

This review summarizes recent progress in thermodynamic modeling of phase assemblage evolution in magnesia cements. First, the basic principles of thermodynamic modeling are introduced, including the role of ion activity, saturation index, chemical equilibrium, Gibbs free energy minimization, and mass action law. Particular attention is paid to the selection of activity coefficient models, because magnesia cement systems, especially MOC, MOS, and salt-exposed systems, commonly contain highly concentrated electrolyte solutions. Second, this review collects and summarizes the thermodynamic databases currently available for magnesia cements and further discusses their main limitations. The reviewed databases cover M-S-H, MPC, MOS, MOC, and carbonation-related systems, including poorly crystalline M-S-H/M-(A)-S-H gels, magnesium phosphate hydrates, basic magnesium sulfate phases, magnesium oxychloride hydrate phases, and magnesium carbonate hydrates. These data provide the basis for thermodynamic modeling of hydration, modification, salt attack, leaching, and carbonation processes. Nevertheless, important gaps remain in the existing databases. For M-S-H-based systems, thermodynamic data are still insufficient to describe the continuous variation of Mg/Si and Al/Si ratios in M-S-H and M-(A)-S-H gels. For MPC, the thermodynamic data for intermediate phosphate hydrates and retarder-related complexes remain incomplete. For MOS and MOC, more reliable thermodynamic parameters are needed for magnesium sulfate/chloride phases, especially under variable temperature and high-salinity conditions. In addition, the incorporation of silica fume, fly ash, slag, metakaolin, and other industrial by-products introduces Si, Al, Ca, and Fe into magnesium-based systems, potentially leading to M-S-H, M-(A)-S-H, C-S-H, hydrotalcite-like phases, calcium phosphate phases, and other secondary products; however, thermodynamic data for these multicomponent reaction products are still insufficient. For carbonation thermodynamic modeling, further improvement is needed in the thermodynamic data of metastable magnesium carbonate hydrate phases, as well as in the ion interaction parameters for multicomponent Mg-Cl-SO₄-Na-Ca-K-CO₂-H₂O systems. Therefore, future database development should move from the compilation of individual phase data toward internally consistent multicomponent databases that can better represent the complex reaction environments of magnesia cements.

Third, the applications of thermodynamic modeling in different magnesia cement systems are reviewed. For M-S-H, modeling studies show that the Mg/Si ratio strongly controls the equilibrium among M-S-H gel, Mg(OH)₂, and SiO₂. Low Mg/Si systems tend to form silica-rich M-S-H with better chemical stability, whereas high Mg/Si systems are more likely to generate Mg(OH)₂, which may reduce resistance to salt attack and carbonation. The introduction of metakaolin, sodium carbonate, or other aluminosilicate components can further induce M-(A)-S-H gel, hydrotalcite-like phases, Al(OH)₃, and zeolite-type phases. For MPC, thermodynamic modeling reveals that the Mg/PO₄ ratio, pH, phosphate type, and temperature govern the transition from acidic magnesium phosphate phases to intermediate phases and ultimately to more stable struvite-type products. Modeling has also been applied to assess the effects of wollastonite, carbonation, chloride attack, sulfate attack, and seawater exposure on MPC phase assemblages. For MOS, modeling studies indicate that n_MgO/n_MgSO4 and n_H2O/n_MgSO4 ratios strongly affect the formation of 5-1-7, which is closely associated with compressive strength and water resistance. Chemical modifiers, especially citric acid and tartrate species, can alter Mg²⁺ activity and promote the formation of 5-1-7. For MOC, thermodynamic modeling has been widely used to clarify the stability of P3, P5, and Mg(OH)₂ as functions of n_MgO/n_MgCl2, n_H2O/n_MgCl2, temperature, modifiers, carbonation, chloride attack, and sulfate attack. These studies explain why P5 can provide high early strength but tends to decompose into Mg(OH)₂ under leaching or dilution conditions. Finally, carbonation modeling of RMC and other magnesia cements is discussed. The phase composition of magnesium carbonate hydrates is highly sensitive to CO₂ concentration, humidity, temperature, and reaction time. Because full-equilibrium calculations tend to overpredict thermodynamically stable phases such as MgCO₃ or Mg₅(CO₃)₄(OH)₂·4H₂O, metastable equilibrium modeling is often performed by suppressing selected stable phases to better reproduce experimentally observed intermediate products. This approach has been applied to RMC, M-S-H, MPC, and MOC carbonation, revealing the importance of kinetic limitations and environmental boundary conditions.

Overall, thermodynamic modeling has provided important insights into the hydration, modification, salt attack, leaching, carbonation, and durability of magnesia cements. Nevertheless, several limitations remain, including incomplete thermodynamic data for key hydrates and carbonates, insufficient ion interaction parameters for high-salinity multicomponent systems, simplified descriptions of low-crystalline gels and metastable phases, and limited coupling with kinetic processes. Future studies should further improve thermodynamic databases, validate predictions using XRD, TG, NMR, FTIR, SEM/EDS, ICP-OES, and pore solution analysis, and integrate thermodynamic modeling with kinetic, transport, humidity-controlled, and performance models. Such advances will enhance the predictive capability of thermodynamic modeling and support the rational design, durability assessment, and low-carbon applications of magnesia cements.

Summary and Prospects

Thermodynamic modeling has become a useful tool for understanding hydration, phase evolution, modification mechanisms, and the durability of magnesia cements. It can predict stable phases, pore solution chemistry, saturation indices, and phase stability boundaries under defined conditions, providing theoretical support for mix proportion design and performance optimization. Existing thermodynamic modeling studies have investigated the effects of raw-material mix proportions, temperature, modifiers, carbonation, and aggressive ions on the phase assemblages of M-S-H, MPC, MOS, MOC, and RMC systems, and considerable progress has been made in understanding the formation and transformation of M-S-H/M-(A)-S-H gels, magnesium phosphate hydrates, basic magnesium sulfate and chloride hydrate phases, and magnesium carbonate hydrates. However, several limitations remain. Thermodynamic data for M-S-H/M-(A)-S-H gels, magnesium carbonate hydrates, metastable intermediate products, and the temperature-dependent parameters of some hydration products are still incomplete. In addition, high-ionic-strength pore solutions require appropriate activity coefficient models, but Pitzer parameters for multicomponent systems remain insufficient. Moreover, thermodynamic modeling mainly reflects equilibrium or quasi-equilibrium states and cannot directly describe MgO dissolution, nucleation, growth, transport, or early hydration kinetics. Future work should focus on improving thermodynamic databases, refining activity models for high-salinity systems, and coupling thermodynamic modeling with experimental characterization, kinetic modeling, and transport simulations. This will enhance its reliability in guiding material design, durability assessment, and low-carbon applications.

Key words

magnesia cements / phase assemblage / thermodynamic modeling / thermodynamic databases

引用本文

李童, 郭培洋, 刘昌浩, 陈惠苏. 镁质胶凝材料相组成演化的热力学模拟研究进展. 硅酸盐学报, 2026 , 54 (10) : 3530 -3551 . DOI: 10.14062/j.issn.0454-5648.20260326

Tong LI, Peiyang GUO, Changhao LIU, Huisu CHEN. Thermodynamic Modeling of Phase Assemblage Evolution in Magnesia Cements: A Review[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (10) : 3530 -3551 . DOI: 10.14062/j.issn.0454-5648.20260326

基金

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国家自然科学基金资助项目(52278246; 51878152)

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2026年第54卷第10期

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doi: 10.14062/j.issn.0454-5648.20260326

接收时间：2026-05-14
首发时间：2026-10-22
出版时间：2026-09-02

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收稿日期：2026-05-14
修回日期：2026-07-12

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国家自然科学基金资助项目(52278246; 51878152)

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东南大学材料科学与工程学院，重大基础设施工程材料全国重点实验室，南京　211189

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陈惠苏（1973-），男，博士，教授。

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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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