硅酸盐学报

聚硫辛酸微晶纤维杂化材料的设计合成及其对水泥基材料协同增强增韧机制

PDF下载

李慧娜 ¹^,² , 郑淑珍 ¹ , 田庆斌 ¹ , 周春花 ¹ , 李因文 ¹ , 徐守芳 ¹ , 马建峰 ¹^,²

硅酸盐学报 | 水泥基材料增强增韧及其复合材料专题—研究论文 2026,54(5): 1740-1748

收起

硅酸盐学报 |水泥基材料增强增韧及其复合材料专题—研究论文 2026 , 54 (5) : 1740 -1748

聚硫辛酸微晶纤维杂化材料的设计合成及其对水泥基材料协同增强增韧机制

全屏

李慧娜¹^,², 郑淑珍¹, 田庆斌¹, 周春花¹, 李因文¹, 徐守芳¹, 马建峰¹^,²

作者信息

^1．临沂大学化学化工学院，山东临沂 276000

^2．临沂大学材料科学与工程学院，临沂市环保水性功能高分子材料重点实验室，山东临沂 276000

通讯作者:

马建峰（1989—），男，博士，副教授

郑淑珍（1987—），女，博士，副教授。

作者简介:

李慧娜（1999—），女，硕士研究生。

Synergistic Strengthening and Toughening Mechanism for Cement-Based Materials with Polylipoic Acid Microcrystalline Hybrid Fibers

Huina LI¹^,², Shuzhen ZHENG¹, Qingbin TIAN¹, Chunhua ZHOU¹, Yinwen LI¹, Shoufang XU¹, Jianfeng MA¹^,²

Affiliations

^1.College of Chemistry and Chemical Engineering, Linyi University, Linyi 276000, Shandong, China

^2.Material Science and Engineering College of Linyi University, Linyi Environmental Water Functional Polymer Laboratory, Linyi 276000, Shandong, China

Corresponding Author:

MA Jianfeng (1989-), male, Ph.D., Associate Professor. E-mail: m63952289@163.com

ZHENG Shuzhen (1987-), female, Ph.D., Associate Professor. E-mail: zhenshuzheng@163.com

LI Huina (1999-), female, Master candidate. E-mail: l1070812197@163.com

出版时间: 2026-04-20 doi: 10.14062/j.issn.0454-5648.20250566

文章导航

摘要

收起

单一的有机聚合物或无机纳米材料作为提升水泥基材料力学性能的外加剂已被广泛应用，但材料抗折强度与抗压强度之间的负相关性仍是亟待解决的关键问题。本工作采用有机无机杂化的策略，设计并合成了一种基于动态化学键的聚硫辛酸（PTA）微晶纤维杂化功能材料，该材料能够显著改善水泥基材料的综合力学性能。在制备过程中，利用微晶纤维素（MCC）表面丰富的羟基与线性PTA中的羧酸基团发生酯化反应，实现材料的改性，从而构建起包含可逆共价键（S—S键）以及非共价键（氢键、配位键）等多种相互协同作用的动态聚合物杂化网络。将聚硫辛酸纤维杂化材料（MCPTS）掺入水泥净浆中后，可有效优化其微观结构，显著提高其抗折和抗压性能。具体而言，在较低掺量1.0‰（质量分数）的条件下，加入MCPTS-1的水泥净浆在第3、7、28 d的抗折强度分别较基准微晶纤维素（MCC）提高8.56%、25.91%和22.68%，而其抗压强度在7 d和28 d时分别较基准提高11.80%和6.45%。该研究表明，利用PTA纤维杂化材料调控水泥基材料的微观结构，能够在微纳米尺度上实现物相优化，实现水泥基材料抗折强度和抗压强度的协同提升。

关键词

水泥基材料 / 聚硫辛酸纤维 / 微观结构调控 / 力学性能增强

Abstract

收起

Introduction

Conventional cement-based materials exhibit excellent compressive performance, but are inherently brittle, with inadequate tensile, flexural and deformation capacities, which readily induce cracking and impair the durability and long-term service performance of structures. At present, incorporating organic polymers or inorganic nanomaterials is proven as one of the effective strategies to enhance the mechanical properties of cement-based materials. Organic polymers are widely adopted in cement-based materials for their superior plasticity and toughness. They can adsorb onto the surface of cement particles via electrostatic interaction or hydrogen bonding, changing the hydration process of cement and optimizing the distribution and microstructure of hydration products. In addition, inorganic nanomaterials (e.g., nano-silica, carbon nanotubes and graphene oxide) can also improve the mechanical properties of cement-based materials due to their high specific surface area and reinforcement effect. However, these modification methods have some limitations. For most polymers, their effect on the flexural and compressive strengths of cement-based materials has a negative correlation, and improving the flexural strength can result in a significant reduction in the compressive strength. Furthermore, inorganic nanomaterials suffer from a poor dispersion in cement matrix, which easily causes agglomeration and uneven distribution. In addition, inorganic nanomaterials mainly improve the early compressive performance of cement-based materials, while their enhancement effect on flexural strength is relatively limited. Using organic/inorganic nanocomposites to optimize the microstructures of cement hydration products at the micro/nanometre scale is thus a promising method for improving the mechanical properties of cement-based materials. In this work, α-lipoic acid (TA), a natural bioactive molecule with a five-membered ring disulfide bond, was innovatively introduced and self-polymerized at a high temperature to prepare a dynamic polylipoic acid (PTA) network. Selective esterification modification of reactive hydroxyl groups on microcrystalline cellulose (MCC) molecular chains with PTA could improve MCC dispersibility and endow it with organic polymer characteristics. The prepared PTA-MCC hybrid material exhibited excellent mechanical enhancement in the cement matrix, which can significantly improve the flexural strength of cement-based materials at a low dosage without compromising compressive strength, thus effectively breaking through the technical bottleneck of synergistically enhancing strength and toughness of cement-based materials.

Methods

For the synthesis of polylipoic acid fiber hybrid material (MCPTS), TA powder was weighed according to a selected ratio, reacted in an oil bath at 150 ℃ for 1 h and cooled naturally to obtain linear PTA. The activated MCC and linear PTA were added to DMF solvent in a proportion, fully stirred to form a uniform system, and reacted in an oil bath at 120 ℃ for 6 h. After the reaction, the product was centrifuged and dried by rotary evaporation to obtain the final product of MCPTS. The products were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM), confirming that the activated MCC and linear PTA could be fully combined, and the target hybrid material was prepared.

Results and discussion

The results of mechanical properties of cement paste show that the MCPTS synthesized can effectively improve the comprehensive mechanical properties of cement-based materials, especially a small increase in its compressive strength, which greatly improves the flexural strength of cement-based materials. Under the premise of ensuring that its compressive strength does not decrease, the flexural strength of cement-based materials is synergistically improved. The XRD patterns of cement-based materials at 3-d and 28-d curing ages reveal that the MCPTS-added group promotes cement hydration to a certain extent. Some cement hydration products like calcium hydroxide (CH) and calcium silicate hydrate (C-S-H) gel are formed in the system as the hydration age increases. The SEM images demonstrate that the cement paste has a much denser microstructure with a large number of clustered C-S-H hydration products after the incorporation of MCPTS. The results of cement hydration exothermic tests indicate that cement pastes with MCPTS show a significant hydration acceleration effect, with the occurrence time of their main hydration exothermic peaks advanced to varying degrees and the peak hydration rate increases remarkably.

Conclusions

In this paper, a type of MCPTS hybrid material with dynamic hybrid of PTA and MCC was prepared for a synergistic enhancement of organic-inorganic hybrid. It has reversible covalent bond and non-covalent bond dynamic network structure. The optimal performance was achieved at a dosage of 1.0‰ MCPTS-1. The flexural strength at 3, 7 d and 28 d was increased by 8.56%, 25.91% and 22.68%, respectively, and the compressive strength at 7 d and 28 d was enhanced by 11.80% and 6.45%, respectively. The XRD patterns, SEM images and hydration exothermic analysis indicated that MCPTS could accelerate cement hydration, increase heat release, and promote the formation of a denser hydration product structure, thereby improving mechanical properties. The underlying mechanism was mainly as follows, i.e., the carboxylic acid ion network formed by PTA hydrolysis could chelate Ca²⁺ and optimize the structures of CH crystals and C-S-H gels. MCC dispersed stress concentration through the fiber bridging effect. The synergistic effect of the two components realized the performance enhancement of cement-based materials.

Key words

cement-based materials / thiolactone fiber / microstructure control / enhanced mechanical properties

引用本文

李慧娜, 郑淑珍, 田庆斌, 周春花, 李因文, 徐守芳, 马建峰. 聚硫辛酸微晶纤维杂化材料的设计合成及其对水泥基材料协同增强增韧机制. 硅酸盐学报, 2026 , 54 (5) : 1740 -1748 . DOI: 10.14062/j.issn.0454-5648.20250566

Huina LI, Shuzhen ZHENG, Qingbin TIAN, Chunhua ZHOU, Yinwen LI, Shoufang XU, Jianfeng MA. Synergistic Strengthening and Toughening Mechanism for Cement-Based Materials with Polylipoic Acid Microcrystalline Hybrid Fibers[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (5) : 1740 -1748 . DOI: 10.14062/j.issn.0454-5648.20250566

基金

收起

国家自然科学基金(52208250)
山东省自然科学基金(ZR2023MB055; ZR2022QE006)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2026年第54卷第5期

PDF下载

115

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20250566

接收时间：2025-07-20
首发时间：2026-09-20
出版时间：2026-04-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2025-07-20
修回日期：2025-08-14

基金

国家自然科学基金(52208250)

山东省自然科学基金(ZR2023MB055; ZR2022QE006)

作者信息

^1．临沂大学化学化工学院，山东临沂 276000

^2．临沂大学材料科学与工程学院，临沂市环保水性功能高分子材料重点实验室，山东临沂 276000

通讯作者:

马建峰（1989—），男，博士，副教授

郑淑珍（1987—），女，博士，副教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250566

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

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

关闭全屏

BibTeX
EndNote
RefWorks
TxT