Permeable crystalline materials and nano-SiO2 modified cement grout performance and anti-seepage mechanism
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摘要: 为了提升隧道同步注浆材料的抗渗性能，采用水泥基渗透结晶型防水材料-赛柏斯(CCCW-XYPEX)、纳米SiO2(NS)和水泥为主料，聚羧酸高效减水剂(PCS)为添加剂，基于单因素试验，探究了水灰比(W/C)、PCS掺量、XYPEX掺量与NS掺量对水泥注浆材料的结石率、黏度、凝结时间、力学性能及渗透性能的影响规律。同时，利用XRD、SEM和MIP微观技术，分析了复合注浆材料的水化物相、微观形貌及孔隙结构。结果表明：掺入XYPEX与NS后，水泥浆液的结石率达到100%，并缩短了凝结时间。浆液黏度在W/C和PCS掺量条件下最大下降率分别为50.96%和35.64%。当XYPEX∶NS＜3∶1时，NS占据主导地位，浆液黏度上升。W/C从0.4增加到0.5时，试件抗压强度迅速下降。XYPEX掺量小于等于3wt%时，早期强度下降而后期提升。当NS掺量小于等于1wt%时，NS主要提升早期强度。PCS掺量从0.2wt%增加到0.3wt%时，试件的强度有所提升。W/C为0.4和PCS掺量为0.3wt%时，固结体的相对渗透系数最小。XYPEX掺量超过3wt%不利于固结体早期结构发育，NS掺量超过1wt%时，过量的NS则会导致凝胶材料界面尺寸变大，透水性能增加。微观分析表明，复掺3wt%XYPEX与1wt%NS、单掺1wt%NS或3wt%XYPEX均降低了水泥净浆的孔隙率，其中复掺XYPEX与NS减少54.46%。XYPEX和NS通过催化-络合-沉淀能力和纳米填充效应改善了固结体的孔隙结构。Abstract: In order to improve the impermeability of tunnel synchronous grouting materials, the impacts of water-cement ratio (W/C), PCS dosage, XYPEX dosage, and NS dosage on the stone formation rate, viscosity, setting time, mechanical properties, and permeability of cement grout materials were explored based on single-factor experiments, with cementitious capillary crystalline waterproofing materials—XYPEX (CCCW-XYPEX), nano-SiO2 (NS), and cement as the main ingredients, and polycarboxylate superplasticizer (PCS) as an additive. XRD, SEM, and MIP microtechniques were employed to analyze the hydration phases, microscopic morphology, and pore structure of the composite grouting material. The results show that after adding XYPEX and NS, the stone rate of cement slurry reaches 100%, and the setting time is shortened. The maximum decrease rates of slurry viscosity under the conditions of W/C and PCS content are 50.96% and 35.64%, respectively. When XYPEX : NS < 3 : 1, NS dominates and the slurry viscosity increases. When W/C increases from 0.4 to 0.5, the compressive strength of the specimen decreases rapidly. When the content of XYPEX is less than or equal to 3wt%, the early strength decreases and the later strength increases. When the NS content is less than or equal to 1wt%, NS mainly improves the early strength. When the PCS content increases from 0.2wt% to 0.3wt%, the strength of the specimen is improved. When W/C is 0.4 and PCS content is 0.3wt%, the relative permeability coefficient of the consolidated body is the smallest. When the content of XYPEX is more than 3wt%, it is not conducive to the early structural development of the consolidation body. When the NS content exceeds 1wt%, excessive NS will lead to a larger interface size of the gel material and an increase in water permeability. The microscopic analysis shows that the porosity of cement paste is reduced by mixing 3wt% XYPEX and 1wt% NS, single mixing 1wt% NS or 3wt% XYPEX, and the porosity of cement paste is reduced by 54.46% by mixing XYPEX and NS. XYPEX and NS improve the pore structure of the consolidated body through the catalytic-complexation-precipitation ability and nano-filling effect.
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图 1 原材料照片
Figure 1. Raw material photos
NS—Nano-silica; PCS—Polycarboxylate superplasticizer
图 2 不同配合比条件下复合浆液黏度测试结果
Figure 2. Viscosity test results of composite grout under different mixing ratio conditions
图 3 不同配合比条件下复合浆液凝结时间测试结果
Figure 3. Test results of setting time of composite grout under different mixing ratio conditions
图 4 不同配合比条件下复合浆液固结体的UCS测试结果
Figure 4. UCS test results of composite grout consolidated body under different mix proportion conditions
图 5 不同龄期条件下复合浆液固结体的相对渗透系数测试结果
Figure 5. Test results of relative permeability coefficient of composite grout consolidated body under different age conditions
图 6 不同配合比条件下复合浆液固结体XRD测试结果
Figure 6. XRD test results of composite grout consolidation under different mix proportions
图 7 不同配合比条件下复合浆液固结体的SEM图像
Figure 7. SEM images of composite grout consolidation body under different mixing ratio conditions
图 8 不同配合比条件下固结体的孔隙率及累积进退汞量分布情况
Figure 8. Porosity and cumulative mercury distribution of the consolidated body under different mixing ratios
图 9 不同配合比条件下固结体的孔分布及孔体积占比情况
Figure 9. Pore distribution and pore volume ratio of consolidated body under different mixing ratio conditions
图 11 NS与XYPEX活性物质在复合浆液固结体内的防渗作用过程
Figure 11. Anti-seepage process of NS and XYPEX active substances in composite grout consolidation body
表 1 水泥和赛柏斯(XYPEX)的化学成分(wt%)
Table 1. Chemical composition of cement and XYPEX (wt%)
Chemical formula CaO SiO2 Fe2O3 Al2O3 SO3 MgO K2O Na2O Else Cement 64.16 22.45 2.38 5.32 1.86 1.24 1.14 — 1.45 XYPEX 46.74 13.50 1.58 3.47 2.42 3.70 1.18 9.30 18.11 
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表 2 纳米SiO2基本物理性能指标
Table 2. Basic physical properties of nano-SiO2
Color Average particle size/nm Specific surface area/(m2·g−1) SiO2/% White 20 25-200 ≥99.8
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表 3 注浆材料试样配合比(wt%)
Table 3. Grouting material sample ratio (wt%)
Number W/C XYPEX dosage/wt% NS dosage/wt% PCS dosage/wt% Remark WXNP-1 0.3 3 1 0.3 The first group WXNP-2 0.35 3 1 0.3 WXNP-3 0.4 3 1 0.3 WXNP-4 0.45 3 1 0.3 WXNP-5 0.5 3 1 0.3 WXNP-6 0.4 0 1 0.3 The second group
Combined with WXNP-3WXNP-7 0.4 1 1 0.3 WXNP-8 0.4 2 1 0.3 WXNP-9 0.4 4 1 0.3 WXNP-10 0.4 3 0 0.3 The third group
Combined with WXNP-3WXNP-11 0.4 3 0.5 0.3 WXNP-12 0.4 3 1.5 0.3 WXNP-13 0.4 3 2 0.3 WXNP-14 0.4 3 1 0.2 The fourth group
Combined with WXNP-3WXNP-15 0.4 3 1 0.25 WXNP-16 0.4 3 1 0.35 WXNP-17 0.4 3 1 0.4 Notes: WXNP represents the blend matrix, WXNP represents the blend matrix, W represents water-cement ratio, X represents XYPEX, N represents nano-silica, and P represents polycarboxylate superplasticizer; W/C represents water cement ratio.
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表 4 不同配合比条件下复合浆液结石率测试结果
Table 4. Test results of composite grout stone rate under different mixing ratio conditions
Number Stone rate/% Number Stone rate/% WP 88.57 WXNP-9 100 WXNP-1 100 WXNP-10 100 WXNP-2 100 WXNP-11 100 WXNP-3 100 WXNP-12 100 WXNP-4 100 WXNP-13 100 WXNP-5 100 WXNP-14 100 WXNP-6 100 WXNP-15 100 WXNP-7 100 WXNP-16 100 WXNP-8 100 WXNP-17 100
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