基于热分析的阻燃沥青阻燃机理
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摘要
为了研究阻燃沥青的阻燃机理,采用综合热分析法,对基质沥青、单体阻燃剂、复合阻燃剂及其制备的阻燃沥青和温拌阻燃沥青进行了测试。试验所用的3种单体阻燃剂分别为十溴二苯乙烷(DBDPE)、三氧化二锑(Sb_2O_3)、氢氧化铝(ATH),复合阻燃剂为自制的DBDPE-Sb_2O_3型和DBDPE-Sb_2O_3-ATH型2种阻燃剂,阻燃沥青是采用高速剪切机搅拌各类阻燃剂和基质沥青制备得到,温拌阻燃沥青是在复合阻燃沥青中掺入Sasobit温拌剂制成。通过对比分析各类材料试样的热重(TG)、微商热重(DTG)、差热(DTA)等热分析曲线,提出在沥青中掺入阻燃剂和温拌剂的阻燃机理。研究结果表明:DBDPE以气相阻燃机理为主,兼具凝聚相阻燃作用,主要是通过燃烧产生的溴化氢(HBr)气体消耗沥青反应热解的自由基,从而抑制沥青的燃烧过程;Sb_2O_3在600℃左右升华吸热并分解形成蒸汽,形成毯子效应,发挥一定的气相阻燃作用,因此与DBDPE具有良好的协效阻燃效果,卤-锑复合阻燃沥青的放热曲线斜率较基质沥青有显著降低;ATH主要为吸热阻燃机理,燃烧生成的Al_2O_3具有一定的凝聚相阻燃效果与抑烟作用,阻燃效果在低掺量(掺量小于8%,质量分数,下同)条件下并不明显,但可有效扩大DBDPE-Sb_2O_3复合体系的阻燃温度范围和促进沥青的成炭反应,因此DBDPE-Sb_2O_3-ATH复合阻燃沥青的初始分解温度虽与基质沥青相当,但终止分解温度提高了约100℃,并具有16.5%的残炭率,阻燃效果良好;Sasobit温拌剂掺入后会抑制沥青的成炭反应,对DBDPE-Sb_2O_3-ATH复合阻燃剂的阻燃效果有不利影响。
To study the flame-retardant mechanism of flame-retardant asphalt, a base asphalt, single flame-retardants, composite flame-retardants, flame-retardant asphalt, and warm-mix flame-retardant asphalts which made by the two flame-retardants were studied, based on a comprehensive thermal analysis method. The three single flame-retardants were considered as follows, decabromodiphenyl ethane(DBDPE), antimonous oxide(Sb_2O_3), and aluminum hydroxide(ATH). The two composite flame-retardants applied were a self-developed DBDPE-Sb_2O_3 flame-retardant and a DBDPE-Sb_2O_3-ATH flame-retardant. The flame-retardant asphalts were prepared by mixing the base asphalt and flame-retardants using a high-speed shearing machine. The warm-mix flame-retardant asphalt was prepared by adding a Sasobit warm-mixed agent to the composite flame-retardant asphalt. By comparing and analyzing thermogravimetric(TG), thermogravimetric derivative(DTG), differential thermal analysis(DTA), and other thermal analysis curves of various samples, a flame-retardant mechanism that adding a flame-retardant and a warm-mix agent into the asphalt was presented. The results show that DBDPE is dominated by the gas-phase flame-retardant mechanism, and the flame retardance in a solid phase also plays a role. Hydrogen bromide(HBr)gas is produced, consuming free pyrolysis radicals from the asphalt and restraining the combustion process of the asphalt. Sb_2O_3 forms a blanket effect through sublimation heat absorption and steam formation at approximately 600 ℃, which acts as a gas flame-retardant. Sb_2O_3 and DBDPE achieve a good co-effective flame-retardant mechanism, and the heat curve slope of the Sb_2O_3-DBDPE flame-retardant asphalt decreases significantly compared with the base asphalt. ATH mainly shows a heat-absorbing flame-retardant mechanism. The Al_2O_3 generated by ATH has a condensed phase flame-retardant effect and an anti-smoking effect. The flame-retardant effect of ATH under the conditions of a low dosage(less than 8%, mass fraction, the same below) is not clear. However, it can enlarge the flame-retardant temperature range of the DBDPE-Sb_2O_3 composite flame-retardant and effectively promote a carbonizing reaction of the asphalt. The initial decomposition temperature of the DBDPE-Sb_2O_3-ATH composite flame-retardant asphalt is similar to that of the base asphalt, although the final decomposition temperature increases by approximately 100 ℃ and retains 16.5% of the carbon residue. Therefore, the DBDPE-Sb_2O_3-ATH composite flame-retardant shows a good flame-retardant effect. Sasobit is able to inhibit the carbonated reaction of the asphalt and has an adverse effect on the flame-retardant effect of the DBDPE-Sb_2O_3-ATH flame-retardant.
To study the flame-retardant mechanism of flame-retardant asphalt, a base asphalt, single flame-retardants, composite flame-retardants, flame-retardant asphalt, and warm-mix flame-retardant asphalts which made by the two flame-retardants were studied, based on a comprehensive thermal analysis method. The three single flame-retardants were considered as follows, decabromodiphenyl ethane(DBDPE), antimonous oxide(Sb_2O_3), and aluminum hydroxide(ATH). The two composite flame-retardants applied were a self-developed DBDPE-Sb_2O_3 flame-retardant and a DBDPE-Sb_2O_3-ATH flame-retardant. The flame-retardant asphalts were prepared by mixing the base asphalt and flame-retardants using a high-speed shearing machine. The warm-mix flame-retardant asphalt was prepared by adding a Sasobit warm-mixed agent to the composite flame-retardant asphalt. By comparing and analyzing thermogravimetric(TG), thermogravimetric derivative(DTG), differential thermal analysis(DTA), and other thermal analysis curves of various samples, a flame-retardant mechanism that adding a flame-retardant and a warm-mix agent into the asphalt was presented. The results show that DBDPE is dominated by the gas-phase flame-retardant mechanism, and the flame retardance in a solid phase also plays a role. Hydrogen bromide(HBr)gas is produced, consuming free pyrolysis radicals from the asphalt and restraining the combustion process of the asphalt. Sb_2O_3 forms a blanket effect through sublimation heat absorption and steam formation at approximately 600 ℃, which acts as a gas flame-retardant. Sb_2O_3 and DBDPE achieve a good co-effective flame-retardant mechanism, and the heat curve slope of the Sb_2O_3-DBDPE flame-retardant asphalt decreases significantly compared with the base asphalt. ATH mainly shows a heat-absorbing flame-retardant mechanism. The Al_2O_3 generated by ATH has a condensed phase flame-retardant effect and an anti-smoking effect. The flame-retardant effect of ATH under the conditions of a low dosage(less than 8%, mass fraction, the same below) is not clear. However, it can enlarge the flame-retardant temperature range of the DBDPE-Sb_2O_3 composite flame-retardant and effectively promote a carbonizing reaction of the asphalt. The initial decomposition temperature of the DBDPE-Sb_2O_3-ATH composite flame-retardant asphalt is similar to that of the base asphalt, although the final decomposition temperature increases by approximately 100 ℃ and retains 16.5% of the carbon residue. Therefore, the DBDPE-Sb_2O_3-ATH composite flame-retardant shows a good flame-retardant effect. Sasobit is able to inhibit the carbonated reaction of the asphalt and has an adverse effect on the flame-retardant effect of the DBDPE-Sb_2O_3-ATH flame-retardant.
引文
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[4] 余剑英,罗小锋,吴少鹏,等.阻燃SBS改性沥青的制备及性能[J].中国公路学报,2007,20(2):35-39. YU Jian-ying,LUO Xiao-feng,WU Shao-peng,et al.Preparation and properties of flame-retarded SBS modified asphalt[J].China Journal of Highway and Transport,2007,20(2):35-39.
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[9] 秦先涛,陈拴发,祝斯月,等.沥青路面矿物纤维复合阻燃材料及其热重行为研究[J].公路交通科技,2013,30(12):7-14. QIN Xian-tao,CHEN Shuan-fa,ZHU Si-yue,et al.Composite flame retardant materials with mineral fiber for asphalt pavement and their thermogravimetric behaviors[J].Journal of Highway and Transportation Research and Development,2013,30(12):7-14.
[10] 贺海,王朝辉,刘志胜,等.新型无机阻燃改性沥青的制备与路用性能研究[J].公路交通科技,2014,31(7):45-52. HE Hai,WANG Chao-hui,LIU Zhi-sheng,et al.Study on preparation road performance of new inorganic fire-retardant modified asphalt[J].Journal of Highway and Transportation Research and Development,2014,31(7):45-52.
[11] 王朝辉,李蕊,赵娟娟,等.两种新型无机复合阻燃改性沥青的流变性能及其阻燃机制[J].复合材料学报,2014,31(6):1597-1603. WANG Chao-hui,LI Rui,ZHAO Juan-juan,et al.Rheolaogical properties and retardant mechanisms of two types of new inorganic composite flame retardant modified asphalts[J].Acta Materiae Copmositae Sinica,2014,31(6):1597-1603.
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[13] 陈辉强.新型阻燃沥青的制备及其阻燃机理研究[D].西安:长安大学,2009. CHEN Hui-qiang.Research on preparation and flame-retardant mechanism of fire-retardant asphalt[D].Xi’an:Chang’an University,2009.
[14] 骆建平.温拌阻燃沥青混合料性能研究[D].长沙:长沙理工大学,2014. LUO Jian-ping.The research on the performance of warm mixed antiflaming asphalt mixture[D].Changsha:Changsha University of Science & Technology,2014.
[15] 熊剑平,彭文举.阻燃沥青用十溴二苯乙烷阻燃机理研究[J].交通世界,2016(7/8/9):182-183. XIONG Jian-ping,PENG Wen-ju.Flame retardant mechanism of DBDPE for asphalt[J].Traffic World,2016(7/8/9):182-183.
[16] 徐圣,曾虹燕,赵策,等.镁铝水滑石阻燃剂表面改性及其机理[J].硅酸盐学报,2013,41(4):527-533. XU Sheng,ZENG Hong-yan,ZHAO Ce,et al.Surface modification of Mg-Al hydrotalcite flame-retardant[J].Journal of the Chinese Ceramic Society,2013,41(4):527-533.
[17] 魏建国,李平,付其林,等.一种基于十溴二苯乙烷的沥青混合料用阻燃剂:中国,CN104058625A[P].2014-09-24. WEI Jian-guo,LI Ping,FU Qi-lin,et al.One flame retardant for asphalt mixture based on DBDPE:China,CN104058625A[P].2014-09-24.
[18] 杨洋.一种热分析仪器的专用气氛智能控制模块设计[J].计算机测量与控制,2015,23(1):67-69. YANG Yang.Design of a kind of specialized module applied for thermal analysis insturments[J].Computer Measurement & Control,2015,23(1):67-69.
[19] 吴珂.长隧道火灾湍流燃烧模拟及结构防火安全研究[D].杭州:浙江大学,2008. WU Ke.Turbulent combustion modelling on long tunnel fires and structure fire safey[D].Hangzhou:Zhejiang University,2008.
[20] 李森,王雪,李洪成,等.十溴二苯乙烷阻燃SBR热失重行为研究[J].世界橡胶工业,2014,41(3):24-28. LI Sen,WANG Xue,LI Hong-cheng,et al.Thermogravimetric behaviors of DBDPE flame retardant on SBR[J].World Rubber Industry,2014,41(3):24-28.
[21] 曹新鑫,吕东博,黄海龙,等.氢氧化铝对聚氯乙烯阻燃抑烟改性研究进展[J].中国塑料,2014,28(2):6-11. CAO Xin-xin,LU Dong-bo,HUANG Hai-long,et al.Research progress in flame retardantion and smoke suppression of poly (viny lchloride) modified by aluminium hydroxide[J].China Plastics,2014,28(2):6-11.
[2] 任梵,张晓娇,孙海斌,等.国内外路用阻燃沥青的研究现状与展望[J].长安大学学报:自然科学版,2012,32(6):1-10. REN Fan,ZHANG Xiao-jiao,SUN Hai-bin,et al.Resarch status and development trend of flame-retardant asphalt at home and abroad[J].Journal of Chang’an University:Natural Science Edition,2012,32(6):1-10.
[3] LIU D L,YAN Y Z,HUANG Y Y,et al.Study on flame-retardant properties of flame retardant asphalt mixture[J].Applied Mechanics and Materials,2013(2):387-390.
[4] 余剑英,罗小锋,吴少鹏,等.阻燃SBS改性沥青的制备及性能[J].中国公路学报,2007,20(2):35-39. YU Jian-ying,LUO Xiao-feng,WU Shao-peng,et al.Preparation and properties of flame-retarded SBS modified asphalt[J].China Journal of Highway and Transport,2007,20(2):35-39.
[5] BONATI A,MERUSI F,BCHICCHIO G,et al.Effect of nanocaly and conventional flame retardants on asphalt mixtures fire reaction[J].Construction and Building Materials,2013,47(10):990-1000.
[6] BOURBIGOT S,CERIN O,DUQUESNE S,et al.Flame retardancy bitumen:A calorimetry study[J].Journal of Fire Sciences,2013,31(2):112-130.
[7] 郭进存,廖克俭,戴跃玲.阻燃沥青的研制[J].辽宁石油化工大学学报,2005,25(2):5-8. GUO Jin-cun,LIAO Ke-jian,DAI Yue-ling.Development of asphalt for flame retardancy[J].Journal of Liaoning University of Petroleum & Chemical Technology,2005,25(2):5-8.
[8] 姚洪波.路用阻燃沥青的性能与阻燃机理研究[D].长沙:长沙理工大学,2008. YAO Hong-bo.The research on flame retardant asphalt performance and flame retardant mechanism[D].Changsha:Changsha University of Science & Technology,2008.
[9] 秦先涛,陈拴发,祝斯月,等.沥青路面矿物纤维复合阻燃材料及其热重行为研究[J].公路交通科技,2013,30(12):7-14. QIN Xian-tao,CHEN Shuan-fa,ZHU Si-yue,et al.Composite flame retardant materials with mineral fiber for asphalt pavement and their thermogravimetric behaviors[J].Journal of Highway and Transportation Research and Development,2013,30(12):7-14.
[10] 贺海,王朝辉,刘志胜,等.新型无机阻燃改性沥青的制备与路用性能研究[J].公路交通科技,2014,31(7):45-52. HE Hai,WANG Chao-hui,LIU Zhi-sheng,et al.Study on preparation road performance of new inorganic fire-retardant modified asphalt[J].Journal of Highway and Transportation Research and Development,2014,31(7):45-52.
[11] 王朝辉,李蕊,赵娟娟,等.两种新型无机复合阻燃改性沥青的流变性能及其阻燃机制[J].复合材料学报,2014,31(6):1597-1603. WANG Chao-hui,LI Rui,ZHAO Juan-juan,et al.Rheolaogical properties and retardant mechanisms of two types of new inorganic composite flame retardant modified asphalts[J].Acta Materiae Copmositae Sinica,2014,31(6):1597-1603.
[12] 魏建国,谢成,付其林.阻燃剂对沥青与沥青混合料性能的影响[J].中国公路学报,2013,26(6):30-37. WEI Jian-guo,XIE Cheng,FU Qi-lin.Influence of flame retardant on technical performance of asphalt and asphalt mixture[J].China Journal of Highway and Transport,2013,26(6):30-37.
[13] 陈辉强.新型阻燃沥青的制备及其阻燃机理研究[D].西安:长安大学,2009. CHEN Hui-qiang.Research on preparation and flame-retardant mechanism of fire-retardant asphalt[D].Xi’an:Chang’an University,2009.
[14] 骆建平.温拌阻燃沥青混合料性能研究[D].长沙:长沙理工大学,2014. LUO Jian-ping.The research on the performance of warm mixed antiflaming asphalt mixture[D].Changsha:Changsha University of Science & Technology,2014.
[15] 熊剑平,彭文举.阻燃沥青用十溴二苯乙烷阻燃机理研究[J].交通世界,2016(7/8/9):182-183. XIONG Jian-ping,PENG Wen-ju.Flame retardant mechanism of DBDPE for asphalt[J].Traffic World,2016(7/8/9):182-183.
[16] 徐圣,曾虹燕,赵策,等.镁铝水滑石阻燃剂表面改性及其机理[J].硅酸盐学报,2013,41(4):527-533. XU Sheng,ZENG Hong-yan,ZHAO Ce,et al.Surface modification of Mg-Al hydrotalcite flame-retardant[J].Journal of the Chinese Ceramic Society,2013,41(4):527-533.
[17] 魏建国,李平,付其林,等.一种基于十溴二苯乙烷的沥青混合料用阻燃剂:中国,CN104058625A[P].2014-09-24. WEI Jian-guo,LI Ping,FU Qi-lin,et al.One flame retardant for asphalt mixture based on DBDPE:China,CN104058625A[P].2014-09-24.
[18] 杨洋.一种热分析仪器的专用气氛智能控制模块设计[J].计算机测量与控制,2015,23(1):67-69. YANG Yang.Design of a kind of specialized module applied for thermal analysis insturments[J].Computer Measurement & Control,2015,23(1):67-69.
[19] 吴珂.长隧道火灾湍流燃烧模拟及结构防火安全研究[D].杭州:浙江大学,2008. WU Ke.Turbulent combustion modelling on long tunnel fires and structure fire safey[D].Hangzhou:Zhejiang University,2008.
[20] 李森,王雪,李洪成,等.十溴二苯乙烷阻燃SBR热失重行为研究[J].世界橡胶工业,2014,41(3):24-28. LI Sen,WANG Xue,LI Hong-cheng,et al.Thermogravimetric behaviors of DBDPE flame retardant on SBR[J].World Rubber Industry,2014,41(3):24-28.
[21] 曹新鑫,吕东博,黄海龙,等.氢氧化铝对聚氯乙烯阻燃抑烟改性研究进展[J].中国塑料,2014,28(2):6-11. CAO Xin-xin,LU Dong-bo,HUANG Hai-long,et al.Research progress in flame retardantion and smoke suppression of poly (viny lchloride) modified by aluminium hydroxide[J].China Plastics,2014,28(2):6-11.
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