硅酸盐学报

侧链电离能力对聚羧酸减水剂的硫酸盐耐受性的影响

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管佳男 ¹ , 程博 ¹ , 刘晓 ² , 朱海堂 ¹ , 钱珊珊 ³ , 石建军 ⁴

硅酸盐学报 | 研究论文 2025,53(8): 2320-2327

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硅酸盐学报 |研究论文 2025 , 53 (8) : 2320 -2327

侧链电离能力对聚羧酸减水剂的硫酸盐耐受性的影响

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管佳男¹, 程博¹, 刘晓², 朱海堂¹, 钱珊珊³, 石建军⁴

作者信息

^1．河南工程学院土木工程学院，郑州 451191

^2．北京工业大学材料科学与工程学院，北京 100124

^3．安徽海螺材料科技股份有限公司，安徽芜湖 241000

^4．安徽理工大学化工与爆破学院，安徽淮南 232001

通讯作者:

刘晓（1983—），男，博士，教授。

作者简介:

管佳男（1988—），男，博士，讲师。

Effect of Side Chain Ionizability on Sulfate Tolerance of Polycarboxylate Superplasticizer

Jianan GUAN¹, Bo CHENG¹, Xiao LIU², Haitang ZHU¹, Shanshan QIAN³, Jianjun SHI⁴

Affiliations

^1.College of Civil Engineering, Henan University of Engineering, Zhengzhou 451191, China

^2.College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

^3.Anhui Conch Material Science and Technology Co., Ltd. Wuhu 241000, Anhui, China

^4.School of Chemical and Blasting Engineering, Anhui University of Science & Technology, Huainan 232001, Anhui, China

Corresponding Author:

LIU Xiao (1983-), male, Ph.D., Professor. E-mail: liux@bjut.edu.cn

GUAN Jianan (1988-), male, Ph.D., Lecturer. E-mail: jiananguan@yeah.net

出版时间: 2025-08-20 doi: 10.14062/j.issn.0454-5648.20250016

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摘要

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聚羧酸减水剂（PCE）的侧链电离能力是影响其性能的关键结构参数，然而侧链电离能力发生变化导致PCE对硫酸盐在敏感性（硫酸盐耐受性）方面的影响尚不清楚。本工作基于非电离侧链PCE（NSC-PCE）和可电离侧链PCE（ISC-PCE），通过流动度、流变性能、流体力学半径（R_h）、吸附行为和Zeta电位测试，对比研究了硫酸盐对这两种PCE性能的影响规律。结果表明，提高PCE的侧链电离能力可显著提高其硫酸盐耐受性和浆体的分散稳定性，降低其对硫酸盐竞争吸附和离子强度的敏感性。在此基础上，定量评估了2种PCE的硫酸盐耐受性（ISC-PCE的硫酸盐抗性指数比NSC-PCE提高了32%），并通过全原子分子动力学模拟进行了验证。本研究结果不仅揭示了硫酸盐对PCE性能的影响，还为开发优异相容性的PCE提供了新的方向。

关键词

聚羧酸减水剂 / 侧链电离能力 / 吸附 / 分散性 / 硫酸盐耐受性

Abstract

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Introduction

Polycarboxylate superplasticizer (PCE) is commonly used in cement-based materials, which has the advantages of low dosage, high water reduction and strong molecular designability, which has been widely concerned by many researchers. PCE adsorbs on the surface of cement particles, and then breaks the cement flocculation structure, playing the effect of dispersing cement particles. However, it is known to all that the capacities of dispersing and dispersing retention of PCE to cement slurry are influenced by many parameters, such as cement components and mixing conditions. The polymer adsorption was shown to be very sensitive to the concentration of divalent ions like sulfate ions, so the sulfate ions of the cement slurry appear to be one of the most important parameters that adversely affect performances. In addition, the molecular structure parameters of PCE have an important influence on the adsorption behavior. Therefore, molecular structure parameters are important factors affecting PCE sensitivity to sulfate.

Although previous studies have found that PCE with ionizable side chains (ISC-PCE) has better dispersion retention than PCE with nonionizable side chains (NSC-PCE), the effect of changes in side chain ionizability on its sensitivity to sulfate (sulfate tolerance) is unclear. Therefore, to more effectively realize the performance control of PCE on cement-based materials, the influence of side chain ionizability on sulfate tolerance of PCE is needed. Based on the previously reported ISC-PCE and NSC-PCE, the sulfate concentration was controlled by adding sodium sulfate, under which the new mixed cement slurry flow and its retention and rheological properties were tested to assess the dispersion. The size of PCE in solution, the amount of adsorbed polymer and zeta potential were combined to assess PCE tolerance to SO₄^2-. The salt added species were changed and the effects of SO₄^2- competitive adsorption and ion concentration on PCE performance were analyzed by rheology. The results can help to understand the effect of PCE on cement dispersion in the presence of ion competition and provide a new direction for opening up new structural PCE with good compatibility.

Methods

The fluidities of cement slurries were measured according to the Chinese standard GB/T 8077—2012. A RST-SST rotational rheometer with a paddle rotator of VT40-20 was used (shear rate: 10 s^-1→50 s^-1→10 s^-1). The data was processed with Rheology 3000 software to obtain the yield stress. The hydrodynamic radii (R_h) of the polymers were determined in saline conditions by dynamic light scattering experiments. The adsorbed capacities of the PCEs on cement surfaces, which were calculated from the difference in the concentration of polymers, were measured on a Vario Total Organic Carbon (TOC) analyzer by testing the PCE adsorption after different adsorption times. The zeta potentials of the cement pastes were measured at 25 ℃ on a Malvern Zetasizer Nano ZS90 analyzer. The MD simulations used the Gromacs-4.6.7 software package and a conventional oplsaa force field with RESP charges. The UFF force field was used for the substrate. The equilibrium MD simulation was conducted under the NPT ensemble for a total run time of 20 ns at a relaxed liquid configuration (25 ℃). The solution environment simulations were performed using 3000 water molecules. A relaxation system was selected and the energy was minimized by the steepest descent method with a termination gradient of 100 kJ/(mol·nm) before the relaxation. The system temperature is maintained constant through a Nosé-Hoover thermostat, and periodic boundary conditions were applied to all three dimensions. Long-range electrostatics within a relative tolerance of 1×10^-6 is calculated by the particle mesh Ewald method and a cut-off distance of 1 nm was used as the Ewald interaction and van der Waals interactions. The bond lengths of hydrogen atoms were constrained by the LINCS algorithm. A leap-frog algorithm was used with a time step of 1 fs.

Results and discussion

Compared with no salt, the hydrodynamic radius of NSC-PCE and ISC-PCE decreased by 36.9% (to 8.40 nm) and 8.1% (to 15.98 nm), the cement slurry mobility decreased by 21.7% and 4.3%, the adsorption volume decreased by 21.7% and 3.9%, and the yield stress increased by 42.7% and 27.8%, respectively.

Conclusions

The main conclusions of this paper are summarized as following. The improved side chain ionizability of PCE can significantly improve the dispersion stability and sulfate tolerance, and reduce its sensitivity to sulfate competitive adsorption and ionic strength. Based on the above results, sulfate tolerance of both PCE was quantitatively assessed (the sulfate resistance index of ISC-PCE was increased by 32% as compared to that of NSC-PCE) and verified by all-atom molecular dynamics simulations. The present results not only deepen the understanding of the impact of sulfate on PCE performance, but also provide a new direction for the development of new PCE with good compatibility.

Key words

polycarboxylate superplasticizer / side chain ionizability / adsorption / dispersion / sulfate tolerance

引用本文

管佳男, 程博, 刘晓, 朱海堂, 钱珊珊, 石建军. 侧链电离能力对聚羧酸减水剂的硫酸盐耐受性的影响. 硅酸盐学报, 2025 , 53 (8) : 2320 -2327 . DOI: 10.14062/j.issn.0454-5648.20250016

Jianan GUAN, Bo CHENG, Xiao LIU, Haitang ZHU, Shanshan QIAN, Jianjun SHI. Effect of Side Chain Ionizability on Sulfate Tolerance of Polycarboxylate Superplasticizer[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (8) : 2320 -2327 . DOI: 10.14062/j.issn.0454-5648.20250016

基金

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国家自然科学基金青年基金项目(52302020)
国家自然科学基金面上基金项目(52372020)
安徽博士后科研项目(2025B1078)
河南省科技攻关项目(242102230138)
河南省2024年大学生创新创业训练计划省级项目(202411517010)

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2025年第53卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250016

接收时间：2025-01-06
首发时间：2026-10-21
出版时间：2025-08-20

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出版历史

收稿日期：2025-01-06
修回日期：2025-02-14

基金

国家自然科学基金青年基金项目(52302020)

国家自然科学基金面上基金项目(52372020)

安徽博士后科研项目(2025B1078)

河南省科技攻关项目(242102230138)

河南省2024年大学生创新创业训练计划省级项目(202411517010)

作者信息

^1．河南工程学院土木工程学院，郑州 451191

^2．北京工业大学材料科学与工程学院，北京 100124

^3．安徽海螺材料科技股份有限公司，安徽芜湖 241000

^4．安徽理工大学化工与爆破学院，安徽淮南 232001

通讯作者:

刘晓（1983—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250016

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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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