冻融循环对硅烷改性ECC力学与吸水性能的影响

doi:10.16552/j.cnki.issn1001-1625.2025.1154

摘要/Abstract

摘要：

本文利用多种材料测试技术研究了内掺硅烷类型对工程水泥基复合材料（ECC）力学和吸水性能的影响规律和机理，分析了冻融循环后未改性ECC和内掺异辛基三乙氧基硅烷（IOTS）改性ECC的力学和吸水性能演化规律与微观机制。结果表明：除γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）外，IOTS和N-（β-氨乙基）-γ-氨丙基三甲氧基硅烷（KH792）未对ECC的力学性能产生显著负面影响，KH570和KH792均明显延缓胶凝材料的水化放热。IOTS改性试件表现出最佳的疏水性，且在严重冻融损伤后仍能保持疏水特点。冻融循环后，IOTS改性试件的抗压强度劣化速率高于未改性试件，但其抗折强度更高。随着冻融循环次数的增加，两类试件单位面积吸水质量与时间平方根之间的关系由单线性转变为双线性，且初期线性阶段时长随冻融循环次数的增加而缩短。研究成果能够为ECC的疏水设计及其在冻融环境中的应用和耐久性评价提供理论依据。

关键词: 工程水泥基复合材料, 硅烷改性, 冻融循环, 力学性能, 吸水性能, 低场核磁共振

Abstract:

This study comprehensively investigated the influence patterns and mechanisms of internally incorporated silane types on the mechanical properties and water absorption properties of engineered cementitious composites （ECC） using multiple material testing techniques. It analyzed the evolution patterns and microscopic mechanisms of mechanical and water absorption properties for both unmodified ECC and isooctyl triethoxy silane IOTS modified ECC after freeze-thaw cycles. The results show that： except for γ-methacryloxy propyl trimethoxy silane （KH570）， neither IOTS nor N-（β-aminoethyl）-γ-aminopropyl trimethoxy silane （KH792） causes a significant negative impact on the mechanical properties of ECC. Both KH570 and KH792 markedly delay the hydration heat release of the cementitious materials. The IOTS modified ECC exhibited the best hydrophobicity， maintaining its hydrophobic characteristics even after severe freeze-thaw damage. After freeze-thaw cycles， the compressive strength deterioration rate of IOTS-modified specimens is higher than that of unmodified specimens， but their flexural strength remains higher. As the number of freeze-thaw cycles increases， the relationship between the water absorption mass per unit area and the square root of time shifts from linear to bilinear for both types of specimens， and the duration of the initial linear stage shortens as the number of freeze-thaw cycles increases. The research findings provide a theoretical basis for the hydrophobic design of ECC and its application and durability evaluation in freeze-thaw environments.

Key words: engineered cementitious composite, silane modification, freeze-thaw cycle, mechanical property, water absorption property, low-field nuclear magnetic resonance

中图分类号:

TU528

刘亚君, 薛善彬, 郑子昊, 史志浩, 王文焕. 冻融循环对硅烷改性ECC力学与吸水性能的影响[J]. 硅酸盐通报, 2026, 45(6): 1876-1891.

LIU Yajun, XUE Shanbin, ZHENG Zihao, SHI Zhihao, WANG Wenhuan. Influence of Freeze-Thaw Cycles on Mechanical and Water Absorption Properties of Silane-Modified ECC[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 1876-1891.

图/表 19

表1 普通硅酸盐水泥和粉煤灰的化学成分

Table 1 Chemical composition of ordinary Portland cement and fly ash

Material	Mass fraction/%
Material	SiO₂	Al₂O₃	Fe₂O₃	CaO	SO₃	MgO	Other
Cement	19.5	6.2	5.9	59.4	2.5	3.8	2.7
Fly ash	55.4	28.4	5.1	4.3	1.0	0.9	4.9

图1 三种硅烷的分子结构

Fig.1 Molecular structure of three silanes

表2 三种硅烷的物理化学性质

Table 2 Physicochemical properties of three silanes

Type of silane	IOTS	KH570	KH792
Molecular mass/（g·mol^-1）	276.49	248.35	222.36
Molecular formula	C₁₄H₃₂O₃Si	C₁₀H₂₀O₅Si	C₈H₂₂N₂O₃Si
Density/（g·mL^-1）	0.88	1.045	1.040

表3 工程水泥基复合材料配合比

Table 3 Mix proportion of engineered cementitious composites

Sample No.	Mix proportion/（kg·m^-3）
Sample No.	Cement	Fly ash	Quartz sand	Water	Superplasticizer	PVA fiber	Silane
Unmodified ECC	550	650	550	300	6	23.4	0
Silane modified ECC	550	650	550	300	6	23.4	5.5

图2 试件制备与试验流程图

Fig.2 Specimen preparation and test flow chart

图3 内掺硅烷对不同龄期时ECC力学性能的影响

Fig.3 Effect of silane on mechanical property of ECC at different ages

图4 基于T2谱的ECC微结构及其与力学性能的关联性分析

Fig.4 Analysis of ECC pore structure and its correlation with mechanical property based on T2 spectrum

图5 未改性样品及硅烷改性样品的水化放热监测

Fig.5 Monitoring of hydration heat release of unmodified and silane modified samples

图6 未改性样品及硅烷改性样品的FTIR光谱

Fig.6 FTIR spectra of unmodified and silane modified samples

图7 内掺不同类型硅烷对ECC吸水性能和水分接触角的影响

Fig.7 Effects of different types of silane on water absorption property and water contact angle of ECC

图8 不同次数冻融循环作用后ECC抗压与抗折强度的劣化规律

Fig.8 Deterioration law of compressive and flexural strength of ECC after different freeze-thaw cycles

图9 不同次数冻融循环作用后ECC弹性波波速与相对动弹性模量的演化规律

Fig.9 Evolution of v and Er of ECC after different freeze-thaw cycles

图10 不同次数冻融循环作用后未改性及IOTS改性试件的表观及SEM照片

Fig.10 Appearance and SEM images of unmodified and IOTS-modified specimens after different freeze-thaw cycles

图11 150次冻融循环前后ECC的显微硬度变化

Fig.11 Changes of microhardness of ECC after 150 freeze-thaw cycles

图12 不同次数冻融循环作用后未改性及IOTS改性试件的T2谱及不同类型孔隙体积分数的演化规律

Fig.12 T2 spectrum of unmodified and IOTS-modified specimens after different freeze-thaw cycles and evolution of different types of pore volume fraction

图13 不同次数冻融循环作用后未改性与IOTS改性试件的吸水数据

Fig.13 Water absorption data of unmodified and IOTS-modified specimens after different freeze-thaw cycles

图14 未改性与IOTS改性试件的毛细吸水系数与初期线性吸水阶段时长随冻融循环次数的演化

Fig.14 Evolution of capillary water absorption coefficient and duration of initial linear water absorption phases for unmodified and IOTS-modified specimens with freeze-thaw cycles

图15 冻融循环作用前后试件毛细吸水系数与孔隙度的关联性

Fig.15 Correlation between C and porosity of specimens before and after freeze-thaw cycles

图16 未改性及IOTS改性试件的水分接触角随冻融循环次数的演化

Fig.16 Evolution of water contact angle for unmodified and IOTS-modified specimens with freeze-thaw cycles

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