Effect of capillary crystalline cement additive on the mechanical, anti-chloride ion permeability, and self-healing properties of PE/ECC
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摘要: 为研究无机增殖剂(CCCA)对聚乙烯(PE)纤维增强高延性水泥基复合材料(ECC)力学、抗氯离子渗透及自愈合性能的影响，以PE/ECC为对照组，分别掺入不同质量分数的CCCA (2wt%、4wt%、6wt%、8wt%、10wt%)，通过抗压、抗折、抗拉、电通量法及预加应变损伤法对PE/ECC力学、抗氯离子渗透及自愈合性能进行研究，并利用XRD、SEM-EDS对其自愈合产物进行物相成分、微观形貌及元素组成分析。结果表明：随着CCCA掺量的增加，PE/ECC力学和抗氯离子渗透性能呈先增后减趋势，当CCCA掺量为4wt%时，CCCA对PE/ECC力学和抗氯离子渗透性能整体提升最为明显，抗压、抗折、极限抗拉强度分别提升了55.5%、10.8%、79.4%，极限拉应变变化不大，电通量下降了38.6%。自愈合试验表明，掺入CCCA后，PE/ECC抗拉强度和应变能的恢复率有明显提升，自愈合性能得到了增强。当预损伤应变为0.5%时，掺CCCA的PE/ECC试件抗拉强度和应变能在养护84天后均高于原始基体，较原始基体分别提高10.41%和2.83%。未掺CCCA的PE/ECC试件在3种应变损伤下的抗拉强度和应变能均低于原始基体。XRD和SEM-EDS结果显示，掺CCCA的PE/ECC水化产物中CaCO3、水化硅酸钙(C-S-H)、钙矾石(AFt)衍射峰值强度有所增长，自愈合产物主要是C-S-H晶体，且掺CCCA的PE/ECC中分布更密集。Abstract: To study the effects of capillary crystalline cement additive (CCCA) on the mechanical, chloride ion penetration resistance and self-healing properties of polyethylene (PE) fiber reinforced engineered cementitious composites (ECC), PE/ECC was used as the control group and mixed with different mass fractions of CCCA (2wt%, 4wt%, 6wt%, 8wt%, 10wt%), and the mechanical, anti-chloride ion permeability and self-healing properties of PE/ECC were investigated by compressive, flexural, tensile, electric flux method and pre-loaded strain damage method, and the self-healing products were analyzed by XRD and SEM-EDS for their physical composition, microscopic morphology and elemental composition. The results show that: The mechanical and anti-chloride ion permeability of PE/ECC increase and then decrease with the increase of CCCA doping, and when the doping of CCCA is 4wt%, the mechanical and anti-chloride ion permeability of PE/ECC is most obviously improved by CCCA, and the compressive strength, flexural strength and ultimate tensile stress increase by 55.5%, 10.8%, and 79.4%, respectively. The ultimate tensile strain does not change much, and the electrical flux decreases by 38.6%. The self-healing test shows that the recovery rate of tensile strength and strain energy of PE/ECC is significantly improved after doping with CCCA, and the self-healing performance is enhanced. When the pre-damage strain is 0.5%, the tensile strength and strain energy of PE/ECC specimens doped with CCCA are higher than those of the original matrix after 84 days of maintenance, which are 10.41% and 2.83% higher than those of the original matrix, respectively. The tensile strength and strain energy of PE/ECC specimens without CCCA are lower than those of undamaged specimens under three strain damages. The XRD and SEM-EDS results show that the CaCO3, calcium silicate hydrate (C-S-H), and ettringite (AFt) intensity diffraction peaks increase in the hydration products of PE/ECC with CCCA, and the self-healing products are mainly C-S-H crystals, and the distribution is denser in the PE/ECC with CCCA.
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图 4 不同CCCA掺量的PE/ECC破坏形态
Figure 4. PE/ECC failure morphologies with varying CCCA contents
图 5 不同CCCA掺量的PE/ECC抗压(a)、抗折强度(b)
Figure 5. Compressive (a) and flexural strength (b) of PE/ECC with varying CCCA contents
图 6 不同CCCA掺量的PE/ECC直接拉伸应力-应变曲线
Figure 6. Direct tensile stress-strain curves of PE/ECC with varying CCCA contents
图 7 不同CCCA掺量的PE/ECC抗氯离子性能
Figure 7. Anti-chloride ion permeability of PE/ECC with varying CCCA contents
图 8 不同预损伤PE/ECC试件的拉伸应力-应变曲线
Figure 8. Tensile stress-strain curves of the different pre-damage PE/ECC specimens
The labels represent group (A/S)-the pre-loaded strain level-curing time-pre-loaded (Pre)/re-loaded after healing (Re); e.g. A-0.5%-14Re means the specimen in group A with pre-loaded strain of 0.5% is re-loaded after 14 days of self-healing
图 9 预损愈合试件二次加载应力(σ)-应变(ε)曲线简化图
Figure 9. Simplified stress (σ)-strain (ε) curve of pre-damage healing specimen under secondary loading
图 10 不同PE/ECC试件的拉伸性能参数：((a), (b))抗拉强度；((c), (d))应变能
Figure 10. Characteristics of tensile properties for different PE/ECC specimens: ((a), (b)) Tensile strength; ((c), (d)) Strain energy
图 11 CCCA-PE/ECC和PE/ECC试件裂缝形貌
Figure 11. Microcracks morphology on surface of CCCA-PE/ECC and PE/ECC specimens
图 12 CCCA、PE/ECC和CCCA-PE/ECC试样裂缝自愈合生成物XRD图谱
C-S-H—Calcium silicate hydrate; AFt—Ettringite; CH—Ca(OH)2
Figure 12. XRD patterns of crack self-healing products from CCCA, PE/ECC and CCCA-PE/ECC specimens
图 13 PE/ECC和CCCA-PE/ECC愈合裂纹愈合产物的SEM图像和EDS图谱
Figure 13. SEM images and EDS patterns of healing products in healed crack of PE/ECC and CCCA-PE/ECC
表 1 聚乙烯(PE)纤维性能指标
Table 1. Polyethylene (PE) fiber performance index
Density/
(g·cm−3)Diameter/
mmLength/
mmElastic modulus/
GPa0.97 0.025 18 116 Note: SJ—Sealant for joints. 
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表 2 无机增殖剂(CCCA)化学组成
Table 2. Chemical composition of capillary crystalline cement additive (CCCA)
SiO2/wt% Al2O3/wt% Fe2O3/wt% CaO/wt% MgO/wt% HF/wt% NaCl/wt% SJ/wt% Loss/wt% 73.45 12.50 3.5 2.0 1.5 1.8 0.015 3.00 2.235
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表 3 PE/高延性水泥基复合材料(ECC) 配合比
Table 3. Mix proportions of PE/engineered cementitious composites (ECC)
Sand/(kg·m−3) Cement/(kg·m−3) Fly ash/(kg·m−3) Water/(kg·m−3) HRWR/(kg·m−3) Fiber/(kg·m−3) CCCA/(kg·m−3) 474.4 593.0 711.6 313.1 4.0 19.0 0.0 474.4 593.0 711.6 313.1 4.0 19.0 26.1 474.4 593.0 711.6 313.1 4.0 19.0 52.2 474.4 593.0 711.6 313.1 4.0 19.0 78.3 474.4 593.0 711.6 313.1 4.0 19.0 104.4 474.4 593.0 711.6 313.1 4.0 19.0 130.5 Note: HRWR—High range water reducer.
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表 4 抗拉自愈合试验分组
Table 4. Test grouping of tensile self-healing specimen
Specimen Preloading level Curing time/d S-PL-CT 0.5%/1%/2% 14/28/56/84 A-PL-CT 0.5%/1%/2% 14/28/56/84 Notes: S and A—Experimental group and the control group; PL—Preloading level; CT—Curing time.
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表 5 PE/ECC试件拉伸应变云图
Table 5. Strain nephograms of PE/ECC tensile specimens
CCCA content Initial stage of strain hardening Middle stage of strain hardening Strain softening stage 0wt% 
2wt% 
4wt% 
6wt% 
8wt% 
10wt% 
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