硅酸盐学报

聚合物(AA-AMPS-AM)对硫铝酸盐水泥基注浆材料性能的影响

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李海艳 ¹^,² , 王雨欣 ¹^,² , 张会利 ¹^,² , 管学茂 ¹^,² , 焦华喆 ³

硅酸盐学报 | 研究论文 2026,54(10): 3683-3696

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硅酸盐学报 |研究论文 2026 , 54 (10) : 3683 -3696

聚合物(AA-AMPS-AM)对硫铝酸盐水泥基注浆材料性能的影响

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李海艳¹^,², 王雨欣¹^,², 张会利¹^,², 管学茂¹^,², 焦华喆³

作者信息

^1.河南理工大学，河南省深地材料科学与技术重点实验室，河南　焦作　454000

^2.河南理工大学材料科学与工程学院，河南　焦作　454000

^3.河南理工大学土木工程学院，河南　焦作　454000

作者简介:

李海艳（1983-），女，博士，教授。

Effect of Polymer (AA-AMPS-AM) on Performance of Sulfoaluminate Cement-Based Grouting Materials

Haiyan LI¹^,², Yuxin WANG¹^,², Huili ZHANG¹^,², Xuemao GUAN¹^,², Huazhe JIAO³

Affiliations

^1.Key Laboratory of Materials Science and Technology for Deep Earth, Henan Polytechnic University, Jiaozuo 454000, Henan, China

^2.School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China

^3.School of Civil Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China

LI Haiyan (1983-), female, Ph.D., Professor. E-mail: hpulihy@163.com

出版时间: 2026-07-20 doi: 10.14062/j.issn.0454-5648.20250646

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摘要

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本工作合成了丙烯酸-2-丙烯酰氨基-2-甲基-1-丙烷磺酸-丙烯酰胺聚合物（AA-AMPS-AM），研究聚合物合成过程中链转移剂3-巯基丙酸（MPA）用量对AA-AMPS-AM分子量以及聚合物对硫铝酸盐水泥基注浆材料（SAGMs）水化硬化性能的影响规律。结果表明：随着MPA用量由0.6%（质量分数）降低至0.2%，AA-AMPS-AM的分子量逐渐降低，由124 276 Da降至60 431 Da。SAGMs的初始流动度由345 mm提高至370 mm，并且浆体流动度保持能力显著提高，在60 min时仍然具有100 mm的扩展度。随着AA-AMPS-AM合成过程中MPA用量的降低，初终凝时间延长，抗压强度下降，浆体水化放热速率降低，在水泥颗粒表面的吸附量由4.5 mg/g增至12.5 mg/g。AA-AMPS-AM对主要矿物的溶解及主要产物的形成过程均产生了影响。随着AA-AMPS-AM合成过程中MPA用量的减少，对无水硫酸钙和无水硫铝酸钙矿物的溶解过程的抑制作用增强；钙矾石逐渐由长棒状转变为短柱状且生成量减少，但铝胶生成量增多。基于以上原因，AA-AMPS-AM合成过程中MPA用量的减少，可以有效延缓SAGMs的水化，从而提高了流动度和流动度保持能力。

关键词

硫铝酸盐水泥 / 注浆材料 / 3-巯基丙酸 / 吸附 / 水化 / 流动性能

Abstract

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Introduction

Sulfoaluminate cement-based grouting materials (SAGMs) have emerged as a high-performance solution in modern civil engineering, prized for their rapid setting, high early strength, and volumetric stability in applications ranging from rock reinforcement and concrete crack remediation to mine tunneling support. However, the intrinsic drawback of sulfoaluminate cement-its exceedingly rapid hydration kinetics and short setting times-severely restricts the operational window for grouting operations, challenging the feasibility of large-scale field applications. While chemical admixtures are conventionally employed to disperse cement particles, retard setting, and enhance fluidity to safeguard early-age workability, the distinct mineralogical composition of sulfoaluminate cement (characterized by ye'elimite and anhydrite) compared to ordinary Portland cement creates profound compatibility challenges. Conventional superplasticizers often fail to perform optimally, leading to issues such as flash setting or uncontrolled fluidity loss. Therefore, the rational design of molecularly tailored admixtures specifically compatible with the unique chemistry of SAGMs is of paramount importance. In this study, 3-mercaptopropionic acid (MPA) was utilized as a chain transfer agent to regulate molecular weight during the free radical polymerization of acrylic acid (AA), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), and acrylamide (AM), yielding a series of AA-AMPS-AM. The influence of MPA dosage on polymer architecture was systematically investigated, and the effects of molecular weight variation on the rheological properties, workability retention, and hydration mechanisms of SAGMs were evaluated, with a specific focus on dissolution-precipitation dynamics.

Methods

A suite of AA-AMPS-AM with tailored molecular weights was synthesized by modulating the MPA dosage during aqueous free radical polymerization. The successful synthesis and structural confirmation of these polymers were rigorously verified using Fourier-transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), and proton nuclear magnetic resonance (¹H NMR). The performance of these polymers in SAGMs was quantitatively assessed according to Chinese National Standards: fluidity (GB/T 8077-2012), setting time (GB/T 1346-2011), and mechanical properties of hardened paste (GB/T 7897-2008). To elucidate the interaction mechanisms at the solid-liquid interface, adsorption behavior was probed using zeta potential measurements and total organic carbon (TOC) analysis. The modulation of the hydration process was investigated through the framework of dissolution-precipitation equilibrium, utilizing conductivity measurements and inductively coupled plasma (ICP) spectroscopy to track ionic concentration variations during mineral dissolution. The evolution of key hydration products was analyzed based on these ionic profiles and subsequent solid-phase characterization. Final hydration products were comprehensively identified using X-ray diffraction (XRD), thermogravimetric analysis (TG), laser particle size analysis, and scanning electron microscopy (SEM) for morphological assessment.

Results and Discussion

By maintaining a fixed monomer molar ratio of AA: AMPS: AM = 1:99:30 and adjusting the MPA dosage, water-reducing agents with systematically varied molecular weights were synthesized. Experimental results indicated that reducing the MPA dosage from 0.6% to 0.2% led to a controlled decrease in the molecular weight of AA-AMPS-AM. This molecular tuning significantly enhanced the fluidity of SAGMs; specifically, the incorporation of polymer-2, polymer-4, and polymer-6 increased the initial fluidity to 370, 365 mm, and 345 mm, respectively. Notably, the formulation containing polymer-2 exhibited exceptional fluidity retention, maintaining 100 mm of flowability even after 60 min. Adsorption analysis revealed that lower MPA dosages reduced the polymer's affinity for mineral surfaces, allowing a greater proportion to remain in the liquid phase to act as a steric dispersant. AA-AMPS-AM influenced the hydration process of the SAGMs, a lower MPA dosage strengthened the polymer's inhibitory effect on the dissolution of anhydrous calcium sulfate and calcium sulfoaluminate. This is attributed to AA-AMPS-AM effectively coating the mineral surfaces, creating a physical barrier that limits direct contact with the aqueous solution. Furthermore, AA-AMPS-AM reduced both the rate and total heat release of hydration, with the retarding effect becoming more pronounced at lower MPA contents. The polymers suppressed AFt formation and refined the particle size from 1600 nm to 200 nm, altering AFt morphology from long, slender rods to short, stubby rods. Conversely, lower molecular weight polymers (higher MPA dosage) promoted the formation of an aluminum-rich gel phase, facilitating particle aggregation on the external surface.

Conclusions

This study establishes a clear structure-performance relationship for polymer in SAGMs, demonstrating that molecular architecture-governed by MPA dosage-dictates their efficacy as water reducers and hydration modifiers. Reducing the MPA dosage yields polymers with lower molecular weights and narrower distributions, which optimizes slurry fluidity and effectively retards setting. Crucially, this reduction diminishes polymer adsorption onto cement grains, the resultant increase in free polymer concentration in the pore solution is pivotal for sustaining fluidity. Furthermore, the adsorbed polymer layer acts as a steric barrier that inhibits the dissolution of reactive minerals (anhydrite and ye'elimite), disrupting the dissolution-precipitation equilibrium. This leads to a delayed and modified crystallization of AFt, shifting its morphology from acicular to stubby prismatic crystals. Finally, polymerization conditions favoring lower MPA content promote the co-precipitation of Al(OH)₃ gel alongside the polymer, which encapsulates fine particles and creates a distinctly rough surface topography on the final product.

Key words

sulfoaluminate cement / grouting material / 3-mercaptopropionic acid / adsorption / hydration / fluidity

引用本文

李海艳, 王雨欣, 张会利, 管学茂, 焦华喆. 聚合物(AA-AMPS-AM)对硫铝酸盐水泥基注浆材料性能的影响. 硅酸盐学报, 2026 , 54 (10) : 3683 -3696 . DOI: 10.14062/j.issn.0454-5648.20250646

Haiyan LI, Yuxin WANG, Huili ZHANG, Xuemao GUAN, Huazhe JIAO. Effect of Polymer (AA-AMPS-AM) on Performance of Sulfoaluminate Cement-Based Grouting Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (10) : 3683 -3696 . DOI: 10.14062/j.issn.0454-5648.20250646

基金

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河南省自然科学基金重点项目(262300421255)
河南省自然科学基金面上项目(252300420031)
河南理工大学2025创新研究团队(T2025-3)
河南省科技研发计划联合基金重点项目(235200810016)
河南省深地材料科学与技术重点实验室开放课题(MDE2025-09)

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2026年第54卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250646

接收时间：2025-09-01
首发时间：2026-10-22
出版时间：2026-07-20

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出版历史

收稿日期：2025-09-01
修回日期：2025-11-18

基金

河南省自然科学基金重点项目(262300421255)

河南省自然科学基金面上项目(252300420031)

河南理工大学2025创新研究团队(T2025-3)

河南省科技研发计划联合基金重点项目(235200810016)

河南省深地材料科学与技术重点实验室开放课题(MDE2025-09)

作者信息

^1.河南理工大学，河南省深地材料科学与技术重点实验室，河南　焦作　454000

^2.河南理工大学材料科学与工程学院，河南　焦作　454000

^3.河南理工大学土木工程学院，河南　焦作　454000

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250646

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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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