硅酸盐学报

全冷施工下硬石膏对氯化钙-硫铝酸盐胶凝材料复合体系负温性能的影响

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刘重阳 ¹^,² , 叶家元 ² , 罗凯 ² , 荣辉 ¹ , 任雪红 ² , 陈家俊 ¹^,² , 闫福璐 ² , 陈绍良 ² , 张文生 ² , 罗忠涛 ³

硅酸盐学报 | 研究论文 2026,54(5): 1803-1813

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硅酸盐学报 |研究论文 2026 , 54 (5) : 1803 -1813

全冷施工下硬石膏对氯化钙-硫铝酸盐胶凝材料复合体系负温性能的影响

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刘重阳¹^,², 叶家元², 罗凯², 荣辉¹, 任雪红², 陈家俊¹^,², 闫福璐², 陈绍良², 张文生², 罗忠涛³

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水泥科学与新型建筑材料研究院，北京 100024

^3．郑州大学材料科学与工程学院，郑州 450001

通讯作者:

叶家元（1980—），男，博士，教授。

作者简介:

刘重阳（1998—），男，硕士研究生。

Effect of Anhydrite on Sub-Zero Temperature Properties of Calcium Chloride-Sulfoaluminate Cementitious Composite Systems under Full-Cold Construction

Chongyang LIU¹^,², Jiayuan YE², Kai LUO², Hui RONG¹, Xuehong REN², Jiajun CHEN¹^,², Fulu YAN², Shaoliang CHEN², Wensheng ZHANG², Zhongtao LUO³

Affiliations

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

^2.Cement Science and New Building Materials Academy, China Building Materials Academy Co.,Ltd., Beijing 100024, China

^3.School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China

Corresponding Author:

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

LIU Chongyang (1998-), male, Master candidate. E-mail: chongyangliu909@163.com

出版时间: 2025-10-09 doi: 10.14062/j.issn.0454-5648.20250393

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摘要

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为突破传统热工方法在高寒地区应用中的高能耗与工艺瓶颈，针对氯化钙-硫铝酸盐水泥复合体系在-15 ℃极端环境下水化速率低、早期强度不足的问题，采用全冷施工工艺，通过水化温升、力学性能测试、X射线衍射及热分析等手段，系统研究了硬石膏对其水化放热、力学性能、干缩行为及微观结构的调控机制。揭示了硬石膏通过调控体系Cl/S物质的量比，促进钙矾石形成、抑制Friedel盐生成，从而优化负温水化产物组成与微观结构的协同作用规律。结果表明：硬石膏掺量为10%时，体系水化放热速率显著加快，早期强度大幅提升，1 d和3 d抗压强度分别达20.1 MPa和38.0 MPa，较纯熟料组提升约100%；同时，干缩性能得到优化，5%掺量时3d收缩率降低至0.100%，25%掺量时28 d收缩率较纯熟料组降低35.100%。适宜掺量硬石膏（10%）通过促进水合硫铝酸钙（Aft）形成，有效优化了基体产物结构，赋予该复合体系优异的负温快硬高强与低收缩特性。

关键词

硬石膏 / 负温环境 / 硫铝酸盐水泥 / 水化 / 全冷施工

Abstract

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Introduction

With the continuous expansion of infrastructure construction in alpine regions, a demand for concrete construction under sub-zero temperatures increases significantly. However, conventional low-temperature construction methods suffer from high energy consumption and complex operational processes. Although sulfoaluminate cement (SAC) exhibits excellent low-temperature adaptability, and calcium chloride (as an antifreeze agent) can effectively lower the freezing point and maintain a liquid-phase environment, the hydration kinetics of the simple SAC-calcium chloride composite system under fully cold construction conditions (≤-15 ℃) are severely inhibited at sub-zero temperatures, leading to an insufficient early-age strength development, which fails to meet the rapid construction requirements of engineering projects. Consequently, there is an urgent need to optimize this composite system to fully exploit its rapid hardening and early-strength characteristics under fully cold conditions at -15 ℃.

Anhydrite as a key component of SAC critically regulates the composition of hydration products, microstructure, and macro-scale performance of the cementitious system. However, the existing studies on the effect of anhydrite dosage primarily focus on ambient temperatures or relatively mild sub-zero conditions (e.g., >-5 ℃). Systematic investigations into how anhydrite dosage governs the hydration product evolution, microstructural formation, and mechanical-deformation properties (particularly early-age performance) of the SAC-calcium chloride composite system under extreme low-temperature conditions (-15 ℃) and fully cold construction processes remain largely unexplored.

This study was to systematically reveal the critical regulatory effects and intrinsic mechanisms of anhydrite dosage on the low-temperature hydration and hardening behavior of the SAC-calcium chloride composite system under fully cold construction conditions at -15 ℃, simulating the harsh environments encountered in real-world engineering. The findings could be expected to expand the application potential of SAC in extreme environments, particularly in remote regions lacking thermal energy supply.

Methods

Under fully cold construction conditions (chilled materials, mixing, and curing) at -15 ℃, a composite system was designed with SAC clinker and anhydrite as binders and a 20% calcium chloride solution as a mixing medium. Anhydrite dosage gradients were set at 0%, 5%, 10%, 15%, 20%, 25%, and 30%, respectively.

The mortar specimens (40 mm × 40 mm × 160 mm) were prepared at a water-to-binder ratio of 0.37 based on the standard GB/T 17671—2021 Test Method for Cement Mortar Strength (ISO Method) for strength evaluation. The shrinkage specimens (40 mm × 40 mm × 160 mm) were prepared based on the standard JGJ/T70—2009 for Test Methods of Basic Properties of Construction Mortar.

Cement paste specimens were formulated at a water-to-binder ratio of 0.32. The calcium chloride solution and cement were sequentially poured into a mixer, stirred at a low speed for 120 s, paused for 15 s, and then stirred at a high speed for 120 s. The resultant mixture was cast into molds and compacted by a vibrating table for 60 cycles. All the specimens were cured on racks under uncovered conditions at -15 ℃.

After reaching specified curing ages, the mortar specimens underwent macroscopic tests. Cement paste specimens were crushed on-site, submerged in anhydrous ethanol to terminate hydration at room temperature for ≥7 d, and then vacuum-dried at 40 ℃ and -0.08 MPa for ≥24 h. The dried samples were subjected to the microstructural analyses to investigate the phase composition and hydration mechanisms.

Results and discussion

Under fully cold construction conditions at -15 ℃, the incorporation of 10% anhydrite dosage enables the SAC-calcium chloride composite system to achieve the 1-d and 3-d compressive strengths of 20.1 MPa and 38.0 MPa, respectively, representing approximately 100% enhancement, compared to the pure clinker group. At an anhydrite dosage of 15%, the peak hydration temperature increase reaches 18.9 ℃ (33.9 ℃ relative to ambient temperature), effectively addressing the challenges of delayed early hydration kinetics and insufficient strength in sub-zero environments.

Anhydrite significantly suppresses a shrinkage via promoting the formation of expansive AFt phases. At the dosage of 5%, the 3 d shrinkage rate reduces to 0.100% (i.e., 47.4% reduction), while at the dosage of 25%, the 28 d shrinkage rate decreases to 0.237% (i.e., 35.1% reduction), offering a graded solution for a low-temperature shrinkage control.

The microstructural analyses reveals that anhydrite regulates the types and morphology of hydration products. In the 28 d hydrated pure SAC clinker, unstable petal-like Friedel's salt crystals occur. Anhydrite optimizes the Cl/S ratio of the system, promoting AFt formation, while suppressing Friedel's salt generation. At the optimal dosage of 10%, needle/rod-shaped AFt crystals form a dense interlocking network, which is pivotal for early-age strength enhancement. However, the excessive dosage (>10%) leads to unreacted anhydrite enrichment and short rod-shaped AFt aggregates with localized bridging, resulting in the strength regression at later ages.

Conclusions

Under fully cold construction conditions at -15 ℃, anhydrite significantly enhanced the hydration activity and early-age strength of the SAC-calcium chloride composite system. An appropriate anhydrite dosage of 10% promoted the hydration process of calcium sulfoaluminate in the system and accelerated the nucleation and growth rate of AFt, thereby forming a denser microstructure of early hydration products. However, the excessive anhydrite disrupted the sulfate phase equilibrium in the reaction system, inhibited the continuous formation of AFt, and induced anhydrite enrichment, ultimately degrading the mechanical properties due to structural loosening.

At early ages, the anhydrite dosage of 5% approached the optimal sulfate balance required for hydration, effectively compensating for plastic shrinkage and chemical shrinkage. In contrast, the dosage of 25% provided sufficient SO₄^2- ions during later hydration stages, ensuring sustained AFt formation and suppressing drying shrinkage over time.

Anhydrite optimized the Cl/S molar ratio in the system, facilitating the formation of a dense network of needle-bar Aft, while inhibiting the formation of the unstable Friedel's salt phase. The excessive anhydrite, however, led to interconnected short-rod AFt and gypsum enrichment, further compromising the structural integrity.

Key words

anhydrite / sub-zero temperature environment / sulphoaluminate cement / hydration / full-cold construction

引用本文

刘重阳, 叶家元, 罗凯, 荣辉, 任雪红, 陈家俊, 闫福璐, 陈绍良, 张文生, 罗忠涛. 全冷施工下硬石膏对氯化钙-硫铝酸盐胶凝材料复合体系负温性能的影响. 硅酸盐学报, 2026 , 54 (5) : 1803 -1813 . DOI: 10.14062/j.issn.0454-5648.20250393

Chongyang LIU, Jiayuan YE, Kai LUO, Hui RONG, Xuehong REN, Jiajun CHEN, Fulu YAN, Shaoliang CHEN, Wensheng ZHANG, Zhongtao LUO. Effect of Anhydrite on Sub-Zero Temperature Properties of Calcium Chloride-Sulfoaluminate Cementitious Composite Systems under Full-Cold Construction[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (5) : 1803 -1813 . DOI: 10.14062/j.issn.0454-5648.20250393

基金

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国家“十四五”重点研发计划课题(2022YFC3803102)
国家自然科学基金(52472037)
吴中伟青年科技奖(ZA-137)

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2026年第54卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250393

接收时间：2025-05-19
首发时间：2026-09-20
出版时间：2025-10-09

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收稿日期：2025-05-19
修回日期：2025-06-04

基金

国家“十四五”重点研发计划课题(2022YFC3803102)

国家自然科学基金(52472037)

吴中伟青年科技奖(ZA-137)

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水泥科学与新型建筑材料研究院，北京 100024

^3．郑州大学材料科学与工程学院，郑州 450001

通讯作者:

叶家元（1980—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250393

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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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