硅酸盐学报

不同吸附基团聚羧酸减水剂对半水石膏分散机理

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王学川 ¹ , 王子明 ² , 刘晓 ² , 孙红尧 ³ , 郑春扬 ¹

硅酸盐学报 | 研究论文 2025,53(11): 3227-3238

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硅酸盐学报 |研究论文 2025 , 53 (11) : 3227 -3238

不同吸附基团聚羧酸减水剂对半水石膏分散机理

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王学川¹, 王子明², 刘晓², 孙红尧³, 郑春扬¹

作者信息

^1．江苏奥莱特新材料股份有限公司，江苏省（奥莱特）混凝土高分子助剂工程技术研究中心，南京 211505

^2．北京工业大学材料与制造学部，北京 100124

^3．南京水利科学研究院，南京 210029

作者简介:

王学川（1991—），男，硕士，工程师。

Dispersion Mechanism of Calcium Sulfate Hemihydrate Using Polycarboxylate Superplasticizers with Varied Adsorption Groups

Xuechuan WANG¹, Ziming WANG², Xiao LIU², Hongyao SUN³, Chunyang ZHENG¹

Affiliations

^1.Jiangsu China ARIT New Materials Co., Ltd, Jiangsu Province Engineering Research Center (ARIT) of concrete polymer additives, Nanjing 211505, China

^2.Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing 100124, China

^3.Nanjing Hydraulic Research Institute, Nanjing 210029, China

WANG Xuechuan (1991-), male, master, Engineer. E-mail: aritwxc@163.com

出版时间: 2025-11-20 doi: 10.14062/j.issn.0454-5648.20250281

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摘要

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为阐明不同吸附基团聚羧酸减水剂（PCE）在半水石膏体系中的分散性能与作用机制，合成了3种具有不同吸附基团结构的PCE，分别含羧酸基（PCE-C）、磺酸基（PCE-S）和磷酸基（PCE-P）。通过流动度、吸附量、Zeta电位及分子模拟等手段系统分析其分散性能与界面调控行为。结果表明，PCE-S相较于PCE-C和PCE-P，展现出更高的吸附量、更强的Ca²⁺络合作用、更优的构象展开能力及更显著的SO₄^2-竞争吸附优势，显著提升净浆流动性与24 h抗压强度。尽管磺酸基团吸附能最低，但可诱导石膏（001）表面发生显著电子重排与晶面重构，增强界面协同吸附效应。本研究明确了吸附基团结构对PCE分散机制的调控作用，为石膏专用高性能PCE的分子设计提供理论支撑。

关键词

聚羧酸减水剂 / 吸附基团 / 半水石膏 / 分子动力学模拟 / 竞争吸附 / 表面重构

Abstract

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Introduction

Calcium sulfate hemihydrate is widely used in the construction and industrial fields, and its application effect largely depends on its dispersibility. Early studies mostly used anionic polymer dispersants to improve its performance. Later, with the application of polycarboxylate superplasticizers (PCE) in the cement and concrete fields, the exploration of its application in half-water gypsum began. Research shows that the charge characteristics and side chain structure of PCE have a significant impact on its adsorption behavior and dispersibility. Introducing functional groups using strong complexation ability of Ca²⁺ can improve its dispersibility. However, the mechanism of the influence of PCE molecules' adsorption behavior and dispersibility in calcium sulfate hemihydrate paste with high SO₄^2- concentration and weak acidity is still unclear. Therefore, three types of PCE containing carboxyl groups, sulfonic acid groups and phosphate ester groups were synthesized. Through various means, the dispersibility and interface interaction mechanism of these PCE in the calcium sulfate hemihydrate system were systematically studied, providing a theoretical basis for the development of high-performance PCE molecules.

Methods

Using MAA, SMAS and HEMAP as the main chains, PCEs containing carboxylic acid groups (PCE-C), sulfonic acid groups (PCE-S) and phosphate groups (PCE-P) were synthesized. The synthesized water reducers were subjected to tests such as PCE molecular structure characterization, gypsum paste test, hardened gypsum performance test, simulated gypsum pore solution test, quantum chemical calculation and molecular dynamics simulation.

Results and discussion

Through comprehensive analysis of ¹H NMR spectrum and FTIR spectrum, it can be known that carboxylic acid groups, sulfonic acid groups and phosphate groups were successfully introduced into the three PCEs respectively. GPC showed that the conversion rate of the monomers was above 90%. The performance test of gypsum paste showed that the three water-reducing agents all had dispersing effects on gypsum, among which the dispersing effect and retention effect of PCE-S were the best. After introducing Na₂SO₄ (SS), the influence on the other two water-reducing agents was significant, while PCE-S still showed good fluidity. The water-reducing agents prolonged the setting time of gypsum, while the introduction of SS reduced the setting time of gypsum to a certain extent. PCE-S exhibited better crystal growth regulation ability and had a relatively small impact on the strength of the gypsum hardened paste. The introduction of SS led to a slight decrease in the absolute values of the zeta potential of PCE-S and PCE-P, indicating high adsorption stability in the presence of sodium sulfate. In the adsorption capacity test, PCE-S showed a higher saturated adsorption capacity, and it was least disturbed by SS. The introduction of SS significantly increased the particle size of PCE and broadened the particle size distribution, weakening the electrostatic stability between molecules. The pH titration test showed that PCE-S and PCE-P had higher charge density in the gypsum system. The static charge density distribution of gypsum crystal surfaces showed that the sulfonic acid groups induced obvious electron cloud rearrangement and structural reconstruction on the gypsum surface, and through the "cooperative adsorption effect" induced by surface reconstruction, its macroscopic adsorption capacity and dispersion effect could be significantly enhanced.

Conclusions

The type of PCEs adsorption groups significantly affects its dispersion performance in the calcium sulfate hemihydrate system. PCE-S shows the best improvement in fluidity and resistance to sulfate interference, followed by PCE-P and PCE-C, with the poorest performance. The degree of ionization and apparent charge density of PCE in the calcium sulfate hemihydrate environment play an important regulatory role. PCE-S and PCE-P almost completely ionize at the experimental pH, for both having a higher apparent charge density and enhancing electrostatic adsorption with Ca²⁺ and the degree of molecular unfolding, thereby improving its dispersion stability. The sulfonic acid groups achieve enhanced "cooperative adsorption effect" by inducing significant electronic rearrangement and crystal plane reconstruction on the (001) surface of calcium sulfate hemihydrate, thereby improving its performance in macroscopic adsorption capacity and dispersion properties. Additionally, PCE-S possesses a higher affinity for Ca²⁺, evidenced its stronger complexation capacity and superior competitive adsorption against SO₄^2-. Its increased steric hindrance and high surface coverage further lead to enhanced dispersion efficiency.

Key words

polycarboxylate superplasticizers / adsorption groups / calcium sulfate hemihydrate / molecular dynamics simulations / competitive adsorption / surface reconstruction

引用本文

王学川, 王子明, 刘晓, 孙红尧, 郑春扬. 不同吸附基团聚羧酸减水剂对半水石膏分散机理. 硅酸盐学报, 2025 , 53 (11) : 3227 -3238 . DOI: 10.14062/j.issn.0454-5648.20250281

Xuechuan WANG, Ziming WANG, Xiao LIU, Hongyao SUN, Chunyang ZHENG. Dispersion Mechanism of Calcium Sulfate Hemihydrate Using Polycarboxylate Superplasticizers with Varied Adsorption Groups[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (11) : 3227 -3238 . DOI: 10.14062/j.issn.0454-5648.20250281

基金

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国家发改委重大专项(2024NDRC030200)
江苏省国际合作项目(SBZ2024000068)

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2025年第53卷第11期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250281

接收时间：2025-04-14
首发时间：2026-10-21
出版时间：2025-11-20

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收稿日期：2025-04-14
修回日期：2025-05-05

基金

国家发改委重大专项(2024NDRC030200)

江苏省国际合作项目(SBZ2024000068)

作者信息

^1．江苏奥莱特新材料股份有限公司，江苏省（奥莱特）混凝土高分子助剂工程技术研究中心，南京 211505

^2．北京工业大学材料与制造学部，北京 100124

^3．南京水利科学研究院，南京 210029

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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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