Accelerated aging behavior of glass fiber reinforced methacrylate-based cured-in-place-pipe lining in seawater and sulfuric acid
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摘要: 原位固化管道(Cured-in-place-pipe, CIPP)内衬用于修复被生物硫酸腐蚀的排水管道，也用于市政排海管道。而玻璃纤维/甲基丙烯酸酯基复合材料用于CIPP内衬，在硫酸和海水环境下的耐久性尚不明确。设计了0.5％硫酸、模拟海水与高温(80℃)加速相耦合的老化实验，以纯水作为对照，基于吸水测试、三点弯曲测试、接触角分析、SEM和FTIR等表征测试方法，研究了玻璃纤维/甲基丙烯酸酯基CIPP内衬的老化行为。结果显示：0.5%硫酸、模拟海水和纯水加速老化1440 h后，弯曲强度分别下降了57.9%、58.4%和57.4%，而弯曲模量没有明显下降；酯键水解生成的羟基部分被氧化为羰基，使树脂老化后颜色发黄；硫酸劣化了树脂表面使润湿性降低，也通过腐蚀表面玻璃纤维促进了水分扩散；海水中盐分析出结晶阻碍了水分扩散，也严重破坏了材料表面的树脂层，也使润湿性增强。提高CIPP内衬的耐久性，重点应该抑制水分扩散劣化界面。可为甲基丙烯酸酯用于CIPP修复材料的耐久性评估提供参考依据。Abstract: Cured-in-place-pipe (CIPP) lining is used to repair drainage pipes corroded by biological sulfuric acid and is also used in municipal sea drainage pipes. However, the durability of glass fiber reinforced methacrylate-based composite materials used in CIPP lining in sulfuric acid and seawater environments is unclear. This study established two aging conditions: 0.5% sulfuric acid and simulated seawater, with the temperature of 80°C to accelerate aging. Pure water was used as a control. Characterization and testing methods such as water absorption test, three-point bending test, contact angle analysis, SEM, and FTIR were used for the study to evaluate the aging behavior of glass fiber reinforced methacrylate-based CIPP lining. The results show that the bending strength decreases by 57.9%, 58.4%, and 57.4% respectively, after accelerated aging in 0.5% sulfuric acid, simulated seawater, and pure water for 1440 hours. While the bending modulus does not show a significant decrease. The hydroxyl group generated by the hydrolysis of the ester bond is partially oxidized to a carbonyl group, causing the resin to turn yellow after aging. Sulfuric acid deteriorates the resin surface and reduces the wettability, and also promotes water diffusion by corroding the surface glass fiber. The crystallization of salt in seawater hinders the diffusion of water and severely damages the resin layer on the material surface, leading to enhanced wettability. To enhance CIPP lining durability, efforts should focus on inhibiting moisture diffusion and degradation at the interface. This study can provide a reference basis for the durability evaluation of methacrylate used in CIPP repair materials.
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图 1 玻璃纤维/甲基丙烯酸酯基原位固化管道(CIPP)内衬的固化和切割好的试样
Figure 1. Curing of glass fiber reinforced methacrylate-based cured-in-place-pipe (CIPP) linings and cut specimens
图 2 玻璃纤维/甲基丙烯酸酯基CIPP内衬加速老化后的吸水行为：(a) 增重；(b) 扩散系数和饱和吸水率
Figure 2. Water absorption behavior of glass fiber reinforced methacrylate-based CIPP lining after accelerated aging: (a) Mass gain; (b) Diffusion coefficient and saturated water content
图 3 玻璃纤维/甲基丙烯酸酯基CIPP内衬加速老化后的弯曲强度
Figure 3. Flexural strength of glass fiber reinforced methacrylate-based CIPP lining after accelerated aging
图 4 玻璃纤维/甲基丙烯酸酯基CIPP内衬在三种条件下加速老化后的弯曲应力-应变曲线：(a) 0.5%硫酸；(b) 模拟海水；(c) 纯水
Figure 4. Flexural stress-strain curves of glass fiber reinforced methacrylate-based CIPP lining after accelerated aging under three conditions: (a) 0.5% Sulfuric acid; (b) Simulated seawater; (c) Pure water
图 5 未老化和三种条件下加速老化1440 h后的玻璃纤维/甲基丙烯酸酯基CIPP内衬表面和弯曲断面微观形貌
Figure 5. Micromorphology of the surface and curved cross section of glass fiber reinforced methacrylate-based CIPP lining without aging and after accelerated aging 1440 h under three conditions
图 6 (a) 硫酸和海水腐蚀玻璃纤维/甲基丙烯酸酯基CIPP内衬；(b)树脂/纤维界面劣化；(c)弯曲断裂模式
Figure 6. (a) Sulfuric acid and seawater corrode glass fiber reinforced methacrylate-based CIPP lining; (b) Degradation of resin fiber interface; (c) Bending fracture modes
图 7 未老化和三种条件下加速老化1440 h后的玻璃纤维/甲基丙烯酸酯基CIPP内衬表面FTIR光谱
Figure 7. FTIR spectrum of glass fiber reinforced methacrylate-based CIPP lining without aging and after accelerated aging 1440 h under three conditions.
图 9 (a)玻璃纤维/甲基丙烯酸酯基CIPP内衬加速老化1440 h后的颜色变化；(b)盐壳
Figure 9. (a) The color change of glass fiber reinforced methacrylate-based CIPP lining after accelerated aging 1440 h; (b) Salt crust
图 10 玻璃纤维/甲基丙烯酸酯基CIPP内衬加速老化后的表面接触角
Figure 10. Surface contact angle of glass fiber reinforced methacrylate-based CIPP lining after accelerated aging
表 1 模拟海水成分
Table 1. Simulated seawater composition
Compounds Concentration /(g·L−1) NaCl 24.53 MgCl2 5.20 Na2SO4 4.09 CaCl2 1.16 KCl 0.695 NaHCO3 0.201 KBr 0.101 H3BO3 0.027 SrCl2 0.025 NaF 0.003 
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表 2 玻璃纤维/甲基丙烯酸酯基CIPP内衬加速老化1440 h前后的羰基指数和羟基指数
Table 2. The carbonyl index and hydroxyl index of glass fiber reinforced methacrylate-based CIPP lining before and after accelerated aging1440 h
Carbonyl index Hydroxyl index Before aging Aging 1440 h Before aging Aging 1440 h 0.5% Sulfuric acid 0.560±0.025 0.807±0.026 0±0.01 0.038±0.028 Simulated seawater 0.591±0.019 0.056±0.023 Pure water 0.824±0.021 0.039±0.035
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