Multiscale interfacial characterization and self-healing effect of cementitious materials containing absorbent microcapsules
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摘要: 针对以海藻酸钙为壳、环氧树脂E-51为核的吸水性微胶囊(SA)与水泥基体界面结合力较弱的问题，利用硅烷偶联剂对SA微胶囊表面进行修饰处理，改善其与水泥基体的界面结合，以提升自修复效果。采用SEM、显微硬度和拉拔试验等分析测试手段分别从微观、介观到宏观尺度分析界面结合情况，并通过砂浆试件损伤修复后的抗压强度、抗水渗透性的恢复率来评价自修复效果。研究结果表明，SA经偶联剂KH792修饰处理后，与水泥基体的界面结合更为紧密，界面处显微硬度提高了159%，界面粘结强度提高了67%；掺加4wt%(水泥质量)SA的砂浆，荷载损伤修复后抗压强度恢复率103%，水压损伤修复后抗渗性恢复率达到118%。硅烷偶联剂表面修饰显著提升了SA与水泥基体的界面结合，水泥基材料自修复效果增强。Abstract: Aiming at the problem of weak interfacial binding force between the absorbent microcapsule (SA) with calcium alginate as shell and epoxy resin E-51 as core and cement matrix, silane coupling agent was used to modify the surface of SA microcapsule to improve its interfacial binding with cement matrix, so as to improve the self-healing effect. By means of SEM, microhardness and drawing test, the interface bonding was analyzed from micro, mesoscopic to macro scale, and the self-healing effect was evaluated by the recovery rate of compressive strength and water permeability resistance of the mortar specimen after damage repair. The results show that the interface bond between SA and cement matrix is closer after modification with coupling agent KH792, the microhardness at the interface is increased by 159%, and the interface bond strength is increased by 67%. For the mortar mixed with 4wt% (cement mass) SA, the compressive strength recovery rate after load damage is 103%, and the seepage resistance recovery rate after water pressure damage is 118%. The surface modification of silane coupling agent significantly improved the interface bonding between SA and cement matrix, and the self-healing effect of cement-based materials was enhanced.
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图 1 环氧树脂E-51@海藻酸钙微胶囊(SA)制备示意图
Figure 1. Preparation diagram of epoxy resin E-51@calcium alginate absorbent microcapsule (SA)
图 3 (a) 环氧树脂@海藻酸钙微胶囊(SA)形貌SEM图；(b) 去除核环氧树脂E-51的SA内部SEM图
Figure 3. (a) SEM image of calcium alginate@epoxy resin (SA) morphology; (b) SEM image of the internal SA of nuclear epoxy resin E-51
图 4 硅烷偶联剂修饰后微胶囊表面EDS面扫：(a) KH-1扫描位置；(b) KH-1表面N元素；(c) KH-1表面Si元素; (d) KH-2扫描位置；(e) KH-2表面N元素；(f) KH-2表面Si元素; (g) KH-3扫描位置；(h) KH-3表面N元素；(i) KH-3表面Si元素
Figure 4. EDS surface scan images of microcapsules modified with silane coupling agent: (a) KH-1 scanning position; (b) KH-1 surface N elements; (c) KH-1 surface Si elements; (d) KH-2 scanning position; (e) KH-2 surface N elements; (f) KH-2 surface Si elements; (g) KH-3 scanning position; (h) KH-3 surface N elements; (i) KH-3 surface Si elements
图 5 微胶囊与水泥基体界面结合处形貌SEM图：(a) SA-100X；(b) KH-1-100X；(c) KH-2-100X；(d) KH-3-100X
Figure 5. SEM image of the interface between microcapsule and cement matrix: (a) SA-100X; (b) KH-1-100X; (c) KH-2-100X; (d) KH-3-100X
图 6 SA和KH-3组样品不同位置处的维氏硬度：(a) 测试位置示意图；(b) 维氏硬度
Figure 6. Vickers hardness of SA and KH-3 samples at different locations: (a) Schematic diagram of test locations; (b) Vickers hardness
图 7 掺SA、KH-1、KH-2和KH-3样品的界面粘结强度
Figure 7. Interfacial bonding strength of samples doped with SA, KH-1, KH-2 and KH-3
图 9 水解处理法修饰微胶囊反应示意图
Figure 9. Schematic diagram of the hydrolysis treatment method for modifying microcapsules
图 10 直接处理法修饰微胶囊反应示意图
Figure 10. Schematic diagram of the direct treatment method for modifying microcapsules
图 11 对照组砂浆、掺SA砂浆和掺KH-3砂浆自修复前后的抗压强度
Figure 11. Compressive strength of control group mortar, SA mortar and KH-3 mortar before and after self-repair
图 12 对照组砂浆、掺SA砂浆和掺KH-3砂浆试样自修复前后的抗水渗透性
Figure 12. Water permeability resistance of mortar, SA mortar and KH-3 mortar samples in control group before and after self-repair
表 1 实验所用P.I 42.5硅酸盐水泥的化学成分及熟料矿物组成
Table 1. Chemical composition and clinker mineral composition of P.I 42.5 Portland cement used in the experiment
Constitute SiO2 Fe2O3 CaO MgO SO3 Na2Oeq f-CaO C2S C3S C3A C4AF Content/wt% 22.15 3.12 64.76 2.98 0.65 0.57 0.9 19.01 59.42 6.36 9.48 
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表 2 实验所用 ISO 标准砂粒径分布
Table 2. ISO standard sand particle diameter distribution used in the experiment
Square hole side length/ mm Cumulative screening margin/% Square hole side length/ mm Cumulative screening margin/% 2.0 0 0.5 67±5 1.6 7±5 0.16 87±5 1.0 33±5 0.08 99±1
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表 3 偶联剂处理微胶囊的工艺编号
Table 3. Processing code for coupling agent-treated microcapsules
Serial number Process mode mKH792：mSA KH-1 Hydrolysis method 1∶10 KH-2 Direct method 1∶1 KH-3 Direct method 2∶1
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