化工进展 ›› 2023, Vol. 42 ›› Issue (S1): 328-343.DOI: 10.16085/j.issn.1000-6613.2023-0627
橡胶混凝土界面改性方法及性能提升路径
王家庆1(
), 宋广伟1, 李强1(), 郭帅成2, DAI Qingli3
- 1.南京林业大学土木工程学院，江苏 南京 210037
2.湖南大学土木工程学院，湖南 长沙 410012
3.美国密歇根理工大学土木与环境工程学院，霍顿 密歇根 49931
-
收稿日期:2023-04-18修回日期:2023-05-29出版日期:2023-10-25发布日期:2023-11-30 -
通讯作者:李强 -
作者简介:王家庆（1994—），男，博士，副教授，主要从事可持续交通基础设施材料与结构的研究。E-mail: jiaqingw@njfu.edu.cn。 -
基金资助:国家自然科学基金(52108408);江苏省基础研究计划自然科学基金(BK20210617);长沙理工大学道路结构与材料交通行业重点实验室开放基金(kjf210303)
Rubber-concrete interface modification method and performance enhancement path
WANG Jiaqing1(), SONG Guangwei1, LI Qiang1(), GUO Shuaicheng2, DAI Qingli3
- 1.College of Civil Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
2.School of Civil Engineering, Hunan University, Changsha 410012, Hunan, China
3.School of Civil and Environmental Engineering, Michigan Technological University, Houghton 49931, Michigan, USA
-
Received:2023-04-18Revised:2023-05-29Online:2023-10-25Published:2023-11-30 -
Contact:LI Qiang
摘要：
废旧轮胎固废作为“黑色污染”给我国生态环境带来巨大压力，将废轮胎回收处理并用作水泥混凝土集料可有效降低环境危害并减少对天然资源的开采；针对橡胶集料与水泥石之间界面性能薄弱的难题，对十余种界面改性方法进行分析，总结不同物理、化学改性方法对界面性能及橡胶混凝土力学性能、耐久性的影响规律。通过纤维增韧路径进一步提升橡胶混凝土材料性能，分析钢纤维、玄武岩纤维、聚丙烯纤维和聚乙烯醇纤维等工程常用纤维材料对橡胶混凝土力学性能及抗裂特性的提升效果；研究发现，界面改性能显著改善橡胶-水泥石脆弱界面，提升界面黏结性能。引入纤维可有效提升橡胶混凝土材料的抗裂特性，其中钢纤维复合橡胶混凝土材料力学强度明显提高，改性橡胶集料和纤维复合技术可起到对水泥混凝土材料的“增韧、抗裂”协同提升作用；现有界面改性技术仍存在较多缺点，其对环境的二次污染和改性效率低的问题有待通过对改性技术的进一步优化而解决。纤维复合橡胶混凝土材料的增韧抗裂特性仍有待更深入的探究，针对两者的协同作用机理的研究将阐明纤维复合橡胶混凝土材料的性能优势，可为实际工程应用提供有效的科学依据，进一步扩大废轮胎固废在水泥混凝土材料中的“高值化”利用规模。
中图分类号:
引用本文
王家庆, 宋广伟, 李强, 郭帅成, DAI Qingli. 橡胶混凝土界面改性方法及性能提升路径[J]. 化工进展, 2023, 42(S1): 328-343.
WANG Jiaqing, SONG Guangwei, LI Qiang, GUO Shuaicheng, DAI Qingli. Rubber-concrete interface modification method and performance enhancement path[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 328-343.
图1 近年来汽车保有量与轮胎产量随年份的变化
图1 近年来汽车保有量与轮胎产量随年份的变化
图2 废轮胎橡胶处理工艺流程图
图2 废轮胎橡胶处理工艺流程图
图3 橡胶混凝土相关的工程应用
图3 橡胶混凝土相关的工程应用
图4 橡胶集料表面改性方法
图4 橡胶集料表面改性方法
图5 橡胶混凝土微观界面改性前后的状态对比[33]
图5 橡胶混凝土微观界面改性前后的状态对比[33]
图6 10%橡胶含量的水泥试样断口形貌SEM图像A—橡胶颗粒；B—水泥基体[42]
图6 10%橡胶含量的水泥试样断口形貌SEM图像A—橡胶颗粒；B—水泥基体[42]
图7 橡胶混凝土的水化反应产物微观观测结果[52]
图7 橡胶混凝土的水化反应产物微观观测结果[52]
表1 橡胶混凝土界面改性方法对比分析[27]
| 界面改性方法 | 优点 | 缺点 | 作用机理 | 参考文献 |
|---|---|---|---|---|
| 物理改性 | ||||
| 水洗 | 成本低，环保 | 效果不明显 | 清洗表面杂质，橡胶表面亲水 | [ |
| 预涂胶凝材料 | 材料易得，改性效果较好 | 预涂工艺，复杂耗时 | 提高橡胶集料的弹性模量，橡胶表面亲水 | [ |
| 化学改性 | ||||
| H2SO4 | 改性效果较好 | 处理复杂耗时 | 去除杂质，橡胶表面亲水 | [ |
| KMnO4 | 改性效果较好 | 处理复杂耗时 | 去除杂质，橡胶表面亲水 | [ |
| 硅烷偶联剂 | 改性效果较好 | 危害环境 | 橡胶和水泥基体间形成化学键，橡胶表面亲水 | [ |
| NaOH | 改性效果好，应用广泛 | 处理复杂耗时 | 去除硬脂酸锌和其他杂质，橡胶表面亲水 | [ |
| Ca(OH)2 | 成本低 | 应用不广泛 | 去除杂质，橡胶表面亲水 | [ |
| 部分氧化 | 成本低 | 危害环境，应用不广泛 | 橡胶表面亲水 | [ |
| 胶乳改性 | 改性效果较好，操作方便 | 成本较高 | 促进橡胶与基体之间的黏合、填充效果好 | [ |
| 二硫化碳处理 | 成本低，节省材料 | 有毒 | 橡胶表面亲水，促进水泥水化 | [ |
| 乳化沥青处理 | 改性效果好，经济 | 处理复杂，应用不广泛 | 促进橡胶与基体之间黏合 | [ |
| 丙酮溶液 | 改性效果较好，操作方便 | 有毒，应用不广泛 | 橡胶表面亲水 | [ |
| 紫外线辐射 | 成本低，清洁 | 应用不广泛 | 橡胶表面亲水 | [ |
表1 橡胶混凝土界面改性方法对比分析[27]
| 界面改性方法 | 优点 | 缺点 | 作用机理 | 参考文献 |
|---|---|---|---|---|
| 物理改性 | ||||
| 水洗 | 成本低，环保 | 效果不明显 | 清洗表面杂质，橡胶表面亲水 | [ |
| 预涂胶凝材料 | 材料易得，改性效果较好 | 预涂工艺，复杂耗时 | 提高橡胶集料的弹性模量，橡胶表面亲水 | [ |
| 化学改性 | ||||
| H2SO4 | 改性效果较好 | 处理复杂耗时 | 去除杂质，橡胶表面亲水 | [ |
| KMnO4 | 改性效果较好 | 处理复杂耗时 | 去除杂质，橡胶表面亲水 | [ |
| 硅烷偶联剂 | 改性效果较好 | 危害环境 | 橡胶和水泥基体间形成化学键，橡胶表面亲水 | [ |
| NaOH | 改性效果好，应用广泛 | 处理复杂耗时 | 去除硬脂酸锌和其他杂质，橡胶表面亲水 | [ |
| Ca(OH)2 | 成本低 | 应用不广泛 | 去除杂质，橡胶表面亲水 | [ |
| 部分氧化 | 成本低 | 危害环境，应用不广泛 | 橡胶表面亲水 | [ |
| 胶乳改性 | 改性效果较好，操作方便 | 成本较高 | 促进橡胶与基体之间的黏合、填充效果好 | [ |
| 二硫化碳处理 | 成本低，节省材料 | 有毒 | 橡胶表面亲水，促进水泥水化 | [ |
| 乳化沥青处理 | 改性效果好，经济 | 处理复杂，应用不广泛 | 促进橡胶与基体之间黏合 | [ |
| 丙酮溶液 | 改性效果较好，操作方便 | 有毒，应用不广泛 | 橡胶表面亲水 | [ |
| 紫外线辐射 | 成本低，清洁 | 应用不广泛 | 橡胶表面亲水 | [ |
表2 不同纤维增强橡胶混凝土性能影响规律
纤维 种类 | 橡胶 替代率 | 纤维 体积率/体积掺量 | 抗压强度 变化 | 劈裂抗拉 强度变化 | 抗弯强度 变化 | 其他性能 | 参考文献 |
|---|---|---|---|---|---|---|---|
| 钢纤维 | 5%，10%，15% | 0.5%，0.75%，1% | 掺量＜0.75% 有一定提高 | 随纤维掺量增加 提高8% | 随纤维掺量增加 提高60% | 弹性模量随钢纤维掺量增加而提高 | [ |
| 0，5%，10%，15% | 0，0.5%，1%，1.5% | 0.5%纤维 增长幅度最大 | 1%纤维 提高28% | — | 10%橡胶+1%钢纤维协同作用较好 | [ | |
| 5% | 1%，1.5%，2% | 层布式降低 全掺式稳定 | 层布式稳定 全掺式提高 | 层布式提高 全掺式提高 | 体积率不超过1.5%优选层布式 体积率为2%采用全掺式 | [ | |
| 0，10%，20% | 0，0.25%，0.5%，1% | — | — | — | 纤维用量0~1%时，初始裂纹和最终破坏的抗冲击性分别提高了2.90倍和5.09倍 | [ | |
| 0~35% | 0，0.35%，1% | — | — | — | 抗剪强度提高，缩小裂纹 | [ | |
| 10%，20% | 0.5%，1% | — | — | 随纤维掺量增加提高 | 密度和吸收率略有增加，韧性和耐磨性也显著提高，不影响抗滑性 | [ | |
| 5% | 0，0.5%，1%，1.5% | — | — | — | 提高韧性，初始黏结强度、极限黏结强度等随纤维体积率增加先增大后降低 | [ | |
| 10% | 0，1%，1.5%，2% | 2%纤维 提高26.6% | — | 随纤维掺量增加提高 | 钢纤维对质量损失率的影响为正，对相对动态弹性模量的影响为负 | [ | |
| 5%，10% | 1%，1.5% | 提高 | — | — | 纤维与橡胶取代率的增加导致强度对应的轴向应变和侧向应变的增加 | [ | |
| 10%，15%，25% | 0.2% | — | — | 提高 | 纤维与橡胶结合对提高混凝土的裂纹扩展和耗能具有积极的耦合作用 | [ | |
| 聚乙烯醇纤维 | 15%，20%，25% | 0.5% | 略有降低 | — | 提高 | 改善力学性能，提高断裂能 良好的冻融性能和长期耐久性 | [ |
| 4%，8%，12%，16% | 0.1%，0.3%，0.5%，0.7% | — | — | — | 12%橡胶、0.1%纤维、温度20℃时抗渗性最好 | [ | |
| 5%，10%，15%，20% | 2.4kg/m³ | 28天 强度提高 | — | 降低 | 提高阻尼率，但加剧其界面缺陷 | [ | |
| 5%，10%，15% | 0.1%，0.2%，0.3% | 提高 | 提高 | 提高 | 玄武岩纤维和PVA纤维复合提高了强度 | [ | |
| 10%，20%，30% | 0.1%，0.2%，0.3% | 略有提高 | 提高 | 提高 | 混杂纤维复合对混凝土的劈裂抗拉强度和弯曲强度有积极的影响 | [ | |
| 玄武岩纤维 | 10% | 0.05%，0.1%，0.15%，0.2% | 随纤维掺量增加提高 | — | 随纤维掺量增加提高 | 纤维掺量为0.2%时混凝土强度最大 | [ |
| 5%~30% | 1~5kg/m³ | 1~3kg/m³ 强度提高 | — | — | 提高试件整体性和抗压强度，提高抗冻性能 | [ | |
| 15% | 0.08%，0.10%，0.12% | 0.1%纤维 强度提升最佳 | — | — | 纤维进一步提高抗冲击性能 | [ | |
| 10% | 2kg/m³，4kg/m³ | — | 提高 | 提高 | 较好的强度和变形性能，增韧效果明显 | [ | |
| 0~1% | 0.1% | 提高 | 提高 | — | 提高干缩性和抗冻性 | [ | |
| 10% | 4.56kg/m³ | — | — | 提高 | 提高工作性能 | [ | |
| 聚丙烯纤维 | 2%，6%，10% | 0.1%，0.5%，0.9% | 降低 | 先提高 后降低 | 降低 | 改善韧性，纤维掺量0.5%内最佳 | [ |
| 20% | 0.6kg/m³，1.2kg/m³ | 1.2kg/m³ 提升11.7% | 1.2kg/m³ 提升13.4% | 1.2kg/m³ 提升19.4% | 1.2kg/m³弹性模量提升15.5% | [ | |
| 5%，10% | 1%，2% | 提高 | 提高 | 提高 | 韧性和延性随纤维增加而提升 | [ | |
3%，6%， 9%，12% | 0.1%，0.2%，0.3% | 纤维增加 强度提高 | 略有提高 | 略有提高 | 密度略有提高 | [ |
表2 不同纤维增强橡胶混凝土性能影响规律
纤维 种类 | 橡胶 替代率 | 纤维 体积率/体积掺量 | 抗压强度 变化 | 劈裂抗拉 强度变化 | 抗弯强度 变化 | 其他性能 | 参考文献 |
|---|---|---|---|---|---|---|---|
| 钢纤维 | 5%，10%，15% | 0.5%，0.75%，1% | 掺量＜0.75% 有一定提高 | 随纤维掺量增加 提高8% | 随纤维掺量增加 提高60% | 弹性模量随钢纤维掺量增加而提高 | [ |
| 0，5%，10%，15% | 0，0.5%，1%，1.5% | 0.5%纤维 增长幅度最大 | 1%纤维 提高28% | — | 10%橡胶+1%钢纤维协同作用较好 | [ | |
| 5% | 1%，1.5%，2% | 层布式降低 全掺式稳定 | 层布式稳定 全掺式提高 | 层布式提高 全掺式提高 | 体积率不超过1.5%优选层布式 体积率为2%采用全掺式 | [ | |
| 0，10%，20% | 0，0.25%，0.5%，1% | — | — | — | 纤维用量0~1%时，初始裂纹和最终破坏的抗冲击性分别提高了2.90倍和5.09倍 | [ | |
| 0~35% | 0，0.35%，1% | — | — | — | 抗剪强度提高，缩小裂纹 | [ | |
| 10%，20% | 0.5%，1% | — | — | 随纤维掺量增加提高 | 密度和吸收率略有增加，韧性和耐磨性也显著提高，不影响抗滑性 | [ | |
| 5% | 0，0.5%，1%，1.5% | — | — | — | 提高韧性，初始黏结强度、极限黏结强度等随纤维体积率增加先增大后降低 | [ | |
| 10% | 0，1%，1.5%，2% | 2%纤维 提高26.6% | — | 随纤维掺量增加提高 | 钢纤维对质量损失率的影响为正，对相对动态弹性模量的影响为负 | [ | |
| 5%，10% | 1%，1.5% | 提高 | — | — | 纤维与橡胶取代率的增加导致强度对应的轴向应变和侧向应变的增加 | [ | |
| 10%，15%，25% | 0.2% | — | — | 提高 | 纤维与橡胶结合对提高混凝土的裂纹扩展和耗能具有积极的耦合作用 | [ | |
| 聚乙烯醇纤维 | 15%，20%，25% | 0.5% | 略有降低 | — | 提高 | 改善力学性能，提高断裂能 良好的冻融性能和长期耐久性 | [ |
| 4%，8%，12%，16% | 0.1%，0.3%，0.5%，0.7% | — | — | — | 12%橡胶、0.1%纤维、温度20℃时抗渗性最好 | [ | |
| 5%，10%，15%，20% | 2.4kg/m³ | 28天 强度提高 | — | 降低 | 提高阻尼率，但加剧其界面缺陷 | [ | |
| 5%，10%，15% | 0.1%，0.2%，0.3% | 提高 | 提高 | 提高 | 玄武岩纤维和PVA纤维复合提高了强度 | [ | |
| 10%，20%，30% | 0.1%，0.2%，0.3% | 略有提高 | 提高 | 提高 | 混杂纤维复合对混凝土的劈裂抗拉强度和弯曲强度有积极的影响 | [ | |
| 玄武岩纤维 | 10% | 0.05%，0.1%，0.15%，0.2% | 随纤维掺量增加提高 | — | 随纤维掺量增加提高 | 纤维掺量为0.2%时混凝土强度最大 | [ |
| 5%~30% | 1~5kg/m³ | 1~3kg/m³ 强度提高 | — | — | 提高试件整体性和抗压强度，提高抗冻性能 | [ | |
| 15% | 0.08%，0.10%，0.12% | 0.1%纤维 强度提升最佳 | — | — | 纤维进一步提高抗冲击性能 | [ | |
| 10% | 2kg/m³，4kg/m³ | — | 提高 | 提高 | 较好的强度和变形性能，增韧效果明显 | [ | |
| 0~1% | 0.1% | 提高 | 提高 | — | 提高干缩性和抗冻性 | [ | |
| 10% | 4.56kg/m³ | — | — | 提高 | 提高工作性能 | [ | |
| 聚丙烯纤维 | 2%，6%，10% | 0.1%，0.5%，0.9% | 降低 | 先提高 后降低 | 降低 | 改善韧性，纤维掺量0.5%内最佳 | [ |
| 20% | 0.6kg/m³，1.2kg/m³ | 1.2kg/m³ 提升11.7% | 1.2kg/m³ 提升13.4% | 1.2kg/m³ 提升19.4% | 1.2kg/m³弹性模量提升15.5% | [ | |
| 5%，10% | 1%，2% | 提高 | 提高 | 提高 | 韧性和延性随纤维增加而提升 | [ | |
3%，6%， 9%，12% | 0.1%，0.2%，0.3% | 纤维增加 强度提高 | 略有提高 | 略有提高 | 密度略有提高 | [ |
图8 橡胶混凝土简化细观结构的有限元模拟模型[85]
图8 橡胶混凝土简化细观结构的有限元模拟模型[85]
图9 “天然集料-水泥石”和“橡胶骨料-水泥石”之间界面过渡区差异分析
图9 “天然集料-水泥石”和“橡胶骨料-水泥石”之间界面过渡区差异分析
图10 橡胶-水泥石微观界面电镜扫面图像
图10 橡胶-水泥石微观界面电镜扫面图像
图11 橡胶混凝土界面特性研究的发展方向
图11 橡胶混凝土界面特性研究的发展方向
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