Review on nano clay modified asphalt based on flame retardant and smoke suppression
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摘要: 分析了沥青材料的热解燃烧特性，总结了沥青材料阻燃抑烟性能测试方法，归纳了国内外常用的沥青阻燃剂类型及其优缺点；论述了隧道沥青材料常用的阻燃技术，评析了纳米改性沥青阻燃抑烟机理；探讨了纳米黏土对沥青材料高低温性能、水稳定性及老化性能等路用性能的影响，展望了未来隧道阻燃抑烟沥青材料的研究方向。研究结果表明: 用于隧道沥青材料阻燃剂应具有良好的协同阻燃抑烟效应，而金属氢氧化物和纳米材料具有较大的应用潜力；沥青材料的阻燃抑烟性能测试主要参考聚合物阻燃测试方法，这些试验方法与沥青路面真实燃烧状态明显不符，亟需补充和完善沥青材料阻燃抑烟性能测试方法和标准；以纳米黏土为代表的纳米改性材料对热沥青的烟气释放具有显著的抑制作用，但目前研究主要集中于纳米材料和聚合物复合材料的阻燃机理方面，针对纳米改性沥青的阻燃抑烟机理缺乏系统性研究；纳米黏土可显著改善沥青的高温、水稳及老化性能，对低温性能的影响方面，国内外研究存在较大争议；应将热拌沥青混合料烟气控制技术、金属氢氧化物和纳米黏土协同阻燃技术及沥青材料阻燃性能测试方法等方面作为隧道阻燃抑烟沥青材料未来的重点研究方向。Abstract: The pyrolysis combustion mechanism of asphalt material was analyzed, and the test methods for flame-retardant and smoke-suppression performance of asphalt materials were concluded. The types, advantages, and disadvantages of commonly used asphalt flame retardants in domestic and overseas were investigated. The commonly used flame-retardant technologies of tunnel asphalt materials were studied, and the flame-retardant and smoke-suppression mechanism of nano-modified asphalt was evaluated. The influence of nano-clay on the road performance of asphalt materials was examined in terms of the high- and low-temperature performances, moisture stability, and aging performance. Moreover, the future research directions for flame-retardant and smoke-suppression asphalt materials for tunnels were assessed. Research results show that the flame retardant used in tunnel asphalt materials should have high synergistic flame-retardant and smoke-suppression effects, and the metal hydroxide and nano materials have great application potential. The flame-retardant and smoke-suppression performance testing of asphalt materials mainly includes polymer flame-retardant test methods, but these methods are inconsistent with the actual combustion state of asphalt pavement. Therefore, it is necessary to supplement the flame-retardant and smoke-suppression performance test methods and standards for asphalt materials. Nano-modified materials, such as the nano clay, significantly inhibit the smoke release of hot asphalt. However, current research mainly focuses on the flame-retardant mechanism of nano-materials and polymers, and there is a lack of systematic research on the flame-retardant and smoke-suppression mechanism of nano-modified asphalt. Nano clay significantly improves the high-temperature, moisture stability, and aging performances of asphalt, but there is controversy in the study of low-temperature performance in domestic and overseas. Investigating the technology for the smoke control of hot mix asphalt mixture, metal hydroxide and nano-clay synergistic flame-retardant technology, and flame-retardant performance test methods for asphalt materials should be the focuses of future research on tunnel flame-retardant and smoke-suppression asphalt materials. 3 tabs, 8 figs, 144 refs.
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图 2 沥青材料阻燃抑烟性能测试方法
Figure 2. Test methods for flame retardant and smoke suppression of asphalt materials
图 7 纳米黏土对沥青高温性能的影响
Figure 7. Effects of nano-clay on high temperature performance of asphalt
表 1 沥青阻燃抑烟性能测试方法
Table 1. Test methods of flame retardant and smoke suppression performance of asphalt
测试方法 参考标准 评价指标及标准 优点 缺点 LOI GB/T 2406—2009 小于21%：易燃材料 测试方便，操作简单 由于沥青的高温流体状体，测
试时可操作性差；属于小型燃
烧试验，非真实火灾情况下材
料的易燃性，测试精度不高21%~27%：可燃材料 大于27%：自熄材料 水平垂直燃烧
UL 94GB/T 2408—2008 V-0：高阻燃等级 V-1：低阻燃等级 V-2：最低阻燃等级 锥形量热仪 GB/T 16172—2007 燃烧热释率，点燃时间，燃烧失重，
生烟速率以及CO、CO2浓度等参数接近真实火灾状态下沥青
材料燃烧特性，测试精度高价格昂贵 烟密度 GB 8624—1997 烟密度等级小于等于75 操作简单，测试方便 精度不高，变异性较大 
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表 2 沥青材料阻燃剂
Table 2. Flame retardants of asphalt materials
名称 化合物名称 反应的状态 优点 缺点 有机类 有机卤系 溴系和氯系阻燃剂 固相 掺量少，阻燃效能高；阻燃剂在
燃烧过程中发烟量大，易产生
有毒气体阻燃效率高，对材料的物理机械性能
影响小；缺点是发烟量大、具有一定
毒性，易于水解和热稳定性较差等磷系 红磷、磷酸二氢铵、磷酸氢二铵、
磷酸铵、聚硫酸铵等无机
金属类锑(Sb) 氧化锑 气相 热稳定性好，不产生腐蚀性气体，
阻燃性能持久；其本身存在毒性单独使用阻燃效能较差，
且锑资源有限硼(B) 硼酸锌 液相、固相 热稳定性好，毒性低，消烟 与沥青的相容性较差，一般用作
其他阻燃剂的增效剂铝(Al) 氢氧化铝、三氧化二铝 固相、气相 具有阻燃、填充和抑烟三重功能，
资源丰富，价格低廉其添加量较大，影响沥青的物理力学
性能，与材料的兼容性差镁(Mg) 氢氧化镁 固相、气相 钙(Ca) 氢氧化钙 固相、气相 无机纳米
阻燃剂纳米材料 蒙脱土、累托石、蛭石、
膨胀石墨等固相 资源丰富、制备简单，可提高
沥青材料各项物理力学性能阻燃效果一般，存在一定的
技术问题纳米纤维
阻燃剂碳纳米管、海泡石、
石墨烯等固相 可显著改善沥青材料的各项
物理力学性能但其阻燃效果不佳，需与其他
阻燃剂复配使用
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表 3 OMMT化学成分质量百分数
Table 3. Chemical components mass percents of OMMT
% 化学组成 文献[100] 文献[101] 文献[102] 文献[103] 黏土A 黏土B 有机蒙脱土 有机蒙脱土 黏土A 黏土B 黏土C SiO2 67.60 67.70 60.40 68.71 42.990 0 49.150 0 51.170 0 Al2O3 22.40 23.30 17.91 24.02 8.394 0 8.715 0 9.512 0 Fe2O3 6.30 3.78 1.34 0.67 0.518 9 0.487 5 0.507 8 MgO 2.17 3.03 5.04 0.59 2.174 0 2.089 0 2.152 0 TiO2 0.20 0.48 0.11 2.18 0.043 0 0.043 5 0.050 3 CaO 0.19 0.26 2.49 1.22 0.153 1 0.395 5 0.332 7 K2O 0.13 0.21 0.50 1.12 0.167 2 0.289 6 0.280 7 Na2O 1.06 0.55 0.234 2 0.242 2 0.280 2 ZnO 0.01 0.007 7 0.008 8 0.009 0 灰分 44.720 0 38.000 0 35.250 0
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