硅酸盐学报

高分子增强天然石膏复合材料的制备与性能分析

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马杨豹 ¹^,² , 吴天耀 ¹^,²^,³ , 王泽翔 ¹^,² , 邱祎淼 ¹^,² , 李洒洒 ¹^,² , 崔鑫涛 ¹^,² , 袁新义 ¹^,²

硅酸盐学报 | 研究论文 2026,54(10): 3697-3707

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硅酸盐学报 |研究论文 2026 , 54 (10) : 3697 -3707

高分子增强天然石膏复合材料的制备与性能分析

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马杨豹¹^,², 吴天耀¹^,²^,³, 王泽翔¹^,², 邱祎淼¹^,², 李洒洒¹^,², 崔鑫涛¹^,², 袁新义¹^,²

作者信息

^1.河南工程学院材料工程学院，郑州　450007

^2.河南工程学院河南省纤维制备与改性工程技术研究中心，郑州　450007

^3.昆明理工大学材料科学与工程学院，昆明　650032

作者简介:

马杨豹（1991-），男，博士，讲师。

Preparation and Properties of Natural Gypsum Composites Reinforced with Macromolecular Polymers

Yangbao MA¹^,², Tianyao WU¹^,²^,³, Zexiang WANG¹^,², Yimiao QIU¹^,², Sasa LI¹^,², Xintao CUI¹^,², Xinyi YUAN¹^,²

Affiliations

^1.College of Material Engineering, Henan University of Engineering, Zhengzhou 450007, China

^2.College of Material Engineering, Henan Fiber Preparation and Modification Engineering Technology Research Center, Zhengzhou 450007, China

^3.College of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650032, China

MA Yangbao (1991-), male, Ph.D., Lecturer. E-mail: myb2015dblydx@163.com

出版时间: 2026-07-21 doi: 10.14062/j.issn.0454-5648.20250655

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摘要

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天然石膏凭借其优异的防火、隔热性能在建筑与装饰领域应用广泛，但固有脆性大、强度低、耐磨性差等缺陷严重限制了其在高端场景应用。为解决上述问题，以高分子材料为改性剂，通过系统筛选确定聚乙烯醇（PVA）为最优改性剂，并系统探究0~2%（质量分数）PVA添加量对石膏复合材料可施工性、力学性能、耐磨性能及微观结构的影响规律。实验结果表明：当添加量为1.5%时，材料综合性能达到最优，抗折强度达5.2 MPa、抗压强度达3.4 MPa、表面硬度达16.7 N/mm²，较空白组分别提升344.4%、84.9%和383.0%；粉化率从0.7979%降至0.0545%，耐磨性能显著改善；但PVA对石膏湿态性能正向影响有限。结合XRD、TG及SEM等多维度表征分析可知，适量PVA通过分子链羟基与石膏晶体间的络合及氢键作用，协同发挥“成膜填充-界面桥接-晶体规整化”效应，促进石膏水化进程与晶体取向生长，降低基体孔隙率，提升结构致密性。以简易工艺实现了石膏材料强度与耐磨性的同步提升，为高强耐磨石膏基复合材料的绿色制备与工程应用提供了坚实的理论依据与数据支撑。

关键词

天然石膏 / 聚合物复合材料 / 聚乙烯醇 / 力学性能

Abstract

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Introduction

Natural gypsum is an important inorganic building and decorative material because it offers fire resistance, thermal insulation, acoustic comfort, low energy consumption during processing, and broad resource availability. Nevertheless, the practical upgrading of gypsum products is still constrained by their intrinsic brittleness, low load-bearing capacity, weak surface hardness, and poor resistance to abrasion or surface pulverization. These shortcomings are particularly unfavorable for high-value interior panels, decorative components, and other applications requiring both dimensional stability and long service life. Fiber reinforcement has been widely used to toughen gypsum, but fiber dispersion, reduced slurry workability, increased porosity, and cost or sustainability concerns can limit its application. Therefore, a simple, water-based polymer modification route is necessary to simultaneously improve workability, strength, surface integrity, and durability. In this study, natural gypsum was modified with macromolecular polymers, with the aim of screening an effective modifier and clarifying the relationship between polymer dosage, hydration behavior, microstructure, and macroscopic performance.

Methods

A series of polymer modifiers were first compared, including acrylic emulsion, water-based epoxy AB adhesive, styrene-acrylic emulsion, waterborne polyurethane (WPU), polyvinyl alcohol (PVA), polyacrylamide (PAM), and polyvinylpyrrolidone (PVP). Gypsum slurry was prepared at a gypsum-to-water ratio of 1.0: 0.6 according to the standard consistency requirement. For solid polymers, aqueous polymer solutions were prepared before mixing; for liquid emulsions or adhesives, the solid content was considered when preparing solutions of the required mass fraction. The polymer solution was added into the mixing vessel, gypsum powder was introduced, and the slurry was mixed, cast, vibrated, demolded after final setting, and cured under laboratory conditions. On the basis of preliminary screening, PVA was selected for dosage optimization, and gypsum composites containing 0.0%, 0.5%, 1.0%, 1.5%, and 2.0% (mass fraction) PVA were prepared. Workability was evaluated by spread diameter, initial setting time, and final setting time. Mechanical properties were characterized by flexural strength, compressive strength, and surface hardness, including wet-state tests after water immersion where applicable. Abrasion resistance was assessed using the pulverization rate after rubbing a 30 mm × 30 mm × 30 mm sample against 320-mesh abrasive paper under a constant load. The phase composition, hydration degree, and microstructure were analyzed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), respectively.

Results and Discussion

The screening results showed clear differences among polymer types. PAM, acrylic emulsion, and styrene-acrylic emulsion caused severe loss of spreadability, probably because ionic interaction, flocculation, demulsification, and rapid viscosity growth produced agglomerated slurry systems. PVA, PVP, WPU, and water-based epoxy AB adhesive allowed the slurry to spread, but their effects on workability and setting behavior differed. Among them, PVA produced the most favorable mechanical improvement; at 0.5%, the flexural strength reached 2.3 MPa, 52.9% higher than that of the control sample. PVA was therefore selected as the main modifier.

With increasing PVA dosage, the spread diameter first increased and then decreased. A low PVA content improved particle dispersion through adsorption, electrostatic repulsion, and steric hindrance, whereas excessive PVA formed a three-dimensional network and bound free water through hydrogen bonding, reducing flowability. The initial setting time exhibited a similar first-increase and then decrease trend, while the final setting time decreased slightly overall. This behavior indicates that hydroxyl groups in PVA can interact with calcium ions and delay early nucleation at low dosage, but the water-binding and thickening effects become more pronounced at higher dosage.

The dry mechanical properties reached an optimum at 1.5% PVA. The flexural strength, compressive strength, and surface hardness were 5.2 MPa, 3.4 MPa, and 16.7 N/mm², respectively, representing increases of 344.4%, 84.9%, and 383.0% compared with the blank gypsum. The pulverization rate decreased sharply from 0.7979% to 0.0545%, demonstrating a remarkable enhancement in abrasion resistance. These improvements are attributed to the combined effects of polymer film formation, pore filling, interfacial bridging, and crystal regularization. PVA molecular chains contain abundant hydroxyl groups that can coordinate with calcium ions and form hydrogen bonds with calcium sulfate dihydrate (CaSO₄·2H₂O), thereby strengthening the intercrystalline interface and promoting efficient stress transfer. SEM images confirmed that appropriate PVA addition reduced pores, tightened crystal overlap, and made the fracture surface more compact. XRD patterns showed sharper characteristic peaks of CaSO₄·2H₂O, especially near 31.2°, indicating improved crystal regularity and orientation. TGA further showed that the mass loss associated with dehydration increased from 13.69% in the control sample to 15.89% at 1.5% PVA, suggesting a higher hydration degree and a larger amount of CaSO₄·2H₂O formed. However, when the PVA dosage increased to 2.0%, local polymer-rich agglomerates appeared, free-water diffusion was restricted, hydration and crystal interlocking were weakened, and the mechanical enhancement declined. Wet-state flexural strength, wet compressive strength, and water-immersed hardness changed only slightly, indicating that PVA mainly improves the dry strength and surface wear resistance, while its positive effect on wet-state performance is limited.

Conclusions

PVA is an effective water-soluble polymer modifier for natural gypsum. Compared with other polymer systems, it provides better compatibility between workability and reinforcement. The optimum dosage is 1.5%, at which flexural strength, compressive strength, surface hardness, and abrasion resistance are improved simultaneously. The strengthening mechanism can be summarized as a synergistic film-forming-filling, interfacial-bridging, and crystal-regularizing effect. Appropriate PVA promotes gypsum hydration, improves CaSO₄·2H₂O crystallization, reduces matrix porosity, and enhances crystal bonding. Excessive PVA, however, causes agglomeration, water-binding, increased porosity, and a diluted load-bearing skeleton, resulting in performance deterioration. This simple modification strategy provides a practical route and theoretical basis for preparing high-strength and wear-resistant gypsum-based composites.

Key words

natural gypsum / polymer composite materials / polyvinyl alcohol / mechanical properties

引用本文

马杨豹, 吴天耀, 王泽翔, 邱祎淼, 李洒洒, 崔鑫涛, 袁新义. 高分子增强天然石膏复合材料的制备与性能分析. 硅酸盐学报, 2026 , 54 (10) : 3697 -3707 . DOI: 10.14062/j.issn.0454-5648.20250655

Yangbao MA, Tianyao WU, Zexiang WANG, Yimiao QIU, Sasa LI, Xintao CUI, Xinyi YUAN. Preparation and Properties of Natural Gypsum Composites Reinforced with Macromolecular Polymers[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (10) : 3697 -3707 . DOI: 10.14062/j.issn.0454-5648.20250655

基金

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河南省高等学校重点科研项目(23A430038)
河南工程学院博士培育基金项目(D2022003)
黑龙江省博士后资助项目(LBH-Z23049)

参考文献

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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.0454-5648.20250655

接收时间：2025-09-04
首发时间：2026-10-22
出版时间：2026-07-21

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收稿日期：2025-09-04
修回日期：2025-10-26

基金

河南省高等学校重点科研项目(23A430038)

河南工程学院博士培育基金项目(D2022003)

黑龙江省博士后资助项目(LBH-Z23049)

作者信息

^1.河南工程学院材料工程学院，郑州　450007

^2.河南工程学院河南省纤维制备与改性工程技术研究中心，郑州　450007

^3.昆明理工大学材料科学与工程学院，昆明　650032

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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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