阻燃纤维素/SiO_2纳米复合纤维的研究
摘要
利用湿法纺丝，将硅溶胶分散于粘胶液中，制备阻燃纤维素／SiO_2纳米复合纤维，并研究纳米SiO_2颗粒与纤维素的界面粘结状况，阻燃纤维素／SiO_2纳米复合纤维的纺丝过程、热稳定性、阻燃性以及纤维的各种物理指标。
对硅溶胶及粘胶的结构特点对纺丝原液稳定性的影响进行了分析，讨论了硅溶胶与纤维素间的作用模式。通过对纺丝原液粘度的分析，结果显示SiO_2的添加量、SiO_2和纤维素间的相互作用力及温度共同决定着纤维素／SiO_2混合液的粘度。并采用FT-IR方法及残炭量的测定，证明纤维素与SiO_2能较好的复合，且SiO_2粒子的加入提高了纳米复合材料的结晶性能。
通过TEM、SEM观察无机粒子在纤维中的分散情况。结果表明SiO_2在纤维中以纳米级均匀分散。并对阻燃纤维素／SiO_2纳米复合纤维的单纤维力学性质进行了分析。与粘胶纤维相比，添加无机SiO_2纳米粒子的阻燃纤维素／SiO_2纳米复合纤维的断裂强度降低，断裂伸长提高。
通过粘胶纤维与阻燃纤维素／SiO_2纳米复合纤维的TG／DTG以及DSC分析比较，得出SiO_2的加入增强了纤维素的热稳定性能。阻燃剂SiO_2的加入在一定程度上改变了纤维素的热降解性能，减缓了热降解过程，有利于固相阻燃。利用CONE对阻燃纤维素／SiO_2纳米复合纤维的燃烧过程以及燃烧时热量和烟气的生成量进行了全面的研究。利用PY-GC-MS对粘胶纤维以及阻燃纤维素／SiO_2纳米复合纤维的裂解产物碎片进行研究。并结合利用SEM技术对燃烧残余物的分析，对SiO_2对阻燃纤维素／SiO_2纳米复合纤维的阻燃机理进行探讨。在复合纤维中SiO_2颗粒附近粘附的聚合物分子链具有更高的热稳定性。在高温下阻燃纤维能形成含SiO_2的炭层，在燃烧时起着散热排烟阻挡层的作用。聚硅酸分子能够强烈的催化脱水，并能够增强分子间的交联程度，导致炭化率的提高。
Colloidal silica was mixed with viscose in right proportion and made into flame retardant cellulose/silica nanocomposite fibers by wet spinning. Linking state of the interface between nanopaticals and macromolecules was studied; the structure and the properties of flame retardant cellulose/silica nanocomposite fibers were investigated, including spinning technics, thermal stability, flame retardancy and mechanical properties of fibers. The influence on stability of spinning solution was analyzed by studying the structures of colloidal silica and viscose, and then the structure manner of silica and cellulose was discussed. By analyzing viscosity of spinning solution, we found that: viscosity of spinning solution has relation with silica proportion, interaction of silica and cellulose and temperature of solution. By FT-IR and measuring char contents, a good reaction between cellulose and colloidal silica could be concluded. Crystallization of nanocomposites was increased because of the adding of silica particles.
By observing the morphology of fibers by TEM and SEM, we found that silica can uniformly disperse into regenerated cellulose in nanometer size, and have a better interface with cellulose. At the same time, we also found that the mechanical properties were greatly changed, compared with viscose fiber.
Comparing with viscose fiber by TG/DTG and DSC, we could see that the adding of silica reinforced thermal stability of flame retardant cellulose/silica nanocomposite fibers. In a certain extent, the adding of silica particles changed the thermal pyrolysis and reduced thermal degradation behaviors. We have an extensively research with burning process and its production of heat and smoke of flame retardant cellulose/silica nanocomposite fibers by CONE. The pyrolysis fragments of viscose and flame retardant cellulose/silica nanocomposite fibers were studied by PY-GC-MS. The residua were also studied by SEM. Then we discussed the flame retardant mechanism of SiO_2. The macromolecular chains around silica particles have a high thermal stability. In high temperature, the flame retardant cellulose/silica nanocomposite fibers can form tightly silica char layer, the layer has a function of releasing heat and obstruct. Polysilicic acid can strongly catalyze dehydrate of cellulose, and build up intermoleculars' joinning degree. So the degree of charring can be improved.
对硅溶胶及粘胶的结构特点对纺丝原液稳定性的影响进行了分析，讨论了硅溶胶与纤维素间的作用模式。通过对纺丝原液粘度的分析，结果显示SiO_2的添加量、SiO_2和纤维素间的相互作用力及温度共同决定着纤维素／SiO_2混合液的粘度。并采用FT-IR方法及残炭量的测定，证明纤维素与SiO_2能较好的复合，且SiO_2粒子的加入提高了纳米复合材料的结晶性能。
通过TEM、SEM观察无机粒子在纤维中的分散情况。结果表明SiO_2在纤维中以纳米级均匀分散。并对阻燃纤维素／SiO_2纳米复合纤维的单纤维力学性质进行了分析。与粘胶纤维相比，添加无机SiO_2纳米粒子的阻燃纤维素／SiO_2纳米复合纤维的断裂强度降低，断裂伸长提高。
通过粘胶纤维与阻燃纤维素／SiO_2纳米复合纤维的TG／DTG以及DSC分析比较，得出SiO_2的加入增强了纤维素的热稳定性能。阻燃剂SiO_2的加入在一定程度上改变了纤维素的热降解性能，减缓了热降解过程，有利于固相阻燃。利用CONE对阻燃纤维素／SiO_2纳米复合纤维的燃烧过程以及燃烧时热量和烟气的生成量进行了全面的研究。利用PY-GC-MS对粘胶纤维以及阻燃纤维素／SiO_2纳米复合纤维的裂解产物碎片进行研究。并结合利用SEM技术对燃烧残余物的分析，对SiO_2对阻燃纤维素／SiO_2纳米复合纤维的阻燃机理进行探讨。在复合纤维中SiO_2颗粒附近粘附的聚合物分子链具有更高的热稳定性。在高温下阻燃纤维能形成含SiO_2的炭层，在燃烧时起着散热排烟阻挡层的作用。聚硅酸分子能够强烈的催化脱水，并能够增强分子间的交联程度，导致炭化率的提高。
Colloidal silica was mixed with viscose in right proportion and made into flame retardant cellulose/silica nanocomposite fibers by wet spinning. Linking state of the interface between nanopaticals and macromolecules was studied; the structure and the properties of flame retardant cellulose/silica nanocomposite fibers were investigated, including spinning technics, thermal stability, flame retardancy and mechanical properties of fibers. The influence on stability of spinning solution was analyzed by studying the structures of colloidal silica and viscose, and then the structure manner of silica and cellulose was discussed. By analyzing viscosity of spinning solution, we found that: viscosity of spinning solution has relation with silica proportion, interaction of silica and cellulose and temperature of solution. By FT-IR and measuring char contents, a good reaction between cellulose and colloidal silica could be concluded. Crystallization of nanocomposites was increased because of the adding of silica particles.
By observing the morphology of fibers by TEM and SEM, we found that silica can uniformly disperse into regenerated cellulose in nanometer size, and have a better interface with cellulose. At the same time, we also found that the mechanical properties were greatly changed, compared with viscose fiber.
Comparing with viscose fiber by TG/DTG and DSC, we could see that the adding of silica reinforced thermal stability of flame retardant cellulose/silica nanocomposite fibers. In a certain extent, the adding of silica particles changed the thermal pyrolysis and reduced thermal degradation behaviors. We have an extensively research with burning process and its production of heat and smoke of flame retardant cellulose/silica nanocomposite fibers by CONE. The pyrolysis fragments of viscose and flame retardant cellulose/silica nanocomposite fibers were studied by PY-GC-MS. The residua were also studied by SEM. Then we discussed the flame retardant mechanism of SiO_2. The macromolecular chains around silica particles have a high thermal stability. In high temperature, the flame retardant cellulose/silica nanocomposite fibers can form tightly silica char layer, the layer has a function of releasing heat and obstruct. Polysilicic acid can strongly catalyze dehydrate of cellulose, and build up intermoleculars' joinning degree. So the degree of charring can be improved.
引文
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2．欧育湘，韩廷解．发展阻燃材料，防火灾于未然．新材料产业，2006，10．
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