矿用硅酸盐-多异氰酸酯杂化高分子复合材料安全性能的研究和膨胀传热过程分析

发布时间：2018-01-13 21:02

本文关键词：矿用硅酸盐-多异氰酸酯杂化高分子复合材料安全性能的研究和膨胀传热过程分析　出处：《中国矿业大学》2017年博士论文　论文类型：学位论文

【摘要】：随着我国经济的快速增长和化工行业的迅猛发展,越来越多的高分子聚合物成为了日常应用材料并且也在煤矿生产中担任着重要的角色。但是由于其主要由碳、氧元素构成,极易燃烧,在燃烧时热释放速率大,释放热值高,火焰传播速度快,难熄灭,且绝大多数的高聚物燃烧伴随着浓烟和有毒气体的产生。高分子聚合物燃烧引起的建筑物火灾和煤矿安全生产事故时有发生。本文针对现有高分子聚合物阻燃性能差等缺点,研制了一种杂化高分子复合材料,采用热失重分析,烟密度、燃烧性能测试、压缩和剪切力测试及扫描电子显微镜等手段表征其性能,该杂化高分子复合材料具有阻燃性能优异、力学性能良好等优点,取得的主要成果和结论如下:以无机组份-硅酸钠和有机组份-多异氰酸酯为主要原材料合成了杂化高分子复合材料,探究了不同组分之间力学和阻燃性能的差别。结果表明,杂化高分子复合材料内部引入了稳定的Si-O键和Si-O-Si键。当有机组份和无机组份之间的比例为3:1时,材料的力学性能最为优异。无机组分含量越多,材料的热释放速率和烟气密度越低,但是释放的二氧化碳和一氧化碳量出现波动。表观活化能随着无机组份含量增加和分解率增加不断变大。综合各组样品的力学性能和阻燃性能表现,可以认为无机组份和有机组份的比例为1:3时,最终合成材料的综合性能最为优异。为增强材料的力学性能,提高其安全系数,采用了三种尺寸的空心玻璃微珠和玻璃纤维作为添加剂。探究了不同类型的添加剂和添加量对杂化高分子复合材料性能特别是力学性能的提高效果和阻燃性能的影响规律。结果表明:不同添加剂单独添加都会使材料的最大压缩强度和最大剪切力有所增加,效果最为明显的为玻璃纤维。直径最小的空心玻璃微珠也取得较好效果,并且与玻璃纤维协同使用时效果更佳。四种添加剂都会不同程度的降低材料燃烧时的烟气释放量、热释放速率和热分解速率。综合各组样品的力学性能和阻燃性能表现,可以认为样品GF1.5-320#HGM 3.0 SSP的综合性能最为优异。为了进一步提高材料的阻燃性能,减少材料遇到火焰时受到的破坏,采用了可膨胀石墨作为添加剂。探究了其遇到外部热源时材料的燃烧情况和可膨胀石墨对材料力学性能的影响。结果显示可膨胀石墨的加入使材料的微观结构出现大块破碎颗粒和孔洞,并使材料的脆性增加,降低了其抵抗外部力的能力。但当受到外部热辐射时,可膨胀石墨受热膨胀时在材料表面形成了保护层,降低了材料基体受到的损害。明显的提高了材料的阻燃性能、热稳定性能和表观活化能,此外烟气密度也明显降低。可以发现添加3 wt%可膨胀石墨时,既能很好的提高材料的阻燃性能,又不至于严重破坏材料的力学性能。根据原始杂化高分子复合材料和可膨胀石墨改性杂化高分子复合材料受到热辐射时实际情况,利用有限元分析软件模拟了二者受热过程中内部温度的变化,并进行了对比分析。结果表明含有可膨胀石墨的材料下部温度差异性较小且温度上升较慢,顶部区域温度上升较快,并且下部温度受火焰的影响较小。以杂化高分子复合材料为基础的浆体应用于山西朔州寺尔沟煤矿的围岩巷道加固。结果表明杂化高分子复合材料很好的填充在煤岩裂隙中,增强了煤体的承载能力,并且反应过程产热少,展现了该材料优异的安全性能。
[Abstract]:With the rapid development of China's rapid economic growth and chemical industry, polymer become more and more daily application materials and is also in the coal mine production plays an important role. But because of its mainly composed of carbon, oxygen elements, easy combustion, the combustion heat release rate and release of high calorific value, flame spread fast, difficult to extinguish, and most of the polymer with the burning of smoke and toxic gases produced. Polymer combustion caused the building fire and coal mine production safety accidents have occurred. According to the existing polymer flame retardant performance poor, developed a kind of hybrid polymer composite materials by thermogravimetric analysis, smoke density, combustion performance test, characterization of compression and shear stress test and scanning electron microscopy of the performance of the hybrid polymer composite materials with flame retardant properties Excellent, good mechanical properties and other advantages, the main achievements and conclusions are as follows: using inorganic components and organic components - sodium silicate - polyisocyanate as the main raw material of hybrid polymer composites were synthesized on mechanical and flame retardant properties between different components of the difference. The results show that internal hybrid polymer composite material is introduced the stability of the Si-O and Si-O-Si keys. When between organic and inorganic components ratio was 3:1, the mechanical properties of the material is excellent. The more the content of inorganic components, the heat release rate and smoke density is low, but the amount of carbon dioxide and carbon monoxide release volatility. The apparent activation energy with inorganic the component content and increase the decomposition rate of increase becomes larger and larger. Mechanical properties and flame retardant performance of all samples can be considered comprehensive, inorganic components and organic components ratio was 1:3, and the final yield The comprehensive performance of the material is excellent. In order to enhance the mechanical properties of the material, improve the safety coefficient, the hollow glass beads and three sizes of glass fiber as an additive. To explore the different types of additives and adding special effects of improving the effect of mechanical properties and flame retardant properties on the performance of hybrid polymer composite materials. The results showed that different additives added alone will make the maximum compressive strength and maximum shear stress increase, the most obvious effect for glass fiber. The minimum diameter of hollow glass beads has good effect, better effect and used in conjunction with glass fiber. Four kinds of additives are different reduce the flue gas emissions during combustion of materials, heat release rate and thermal decomposition rate. The mechanical properties and flame retardant performance of each sample can be considered comprehensive, sample GF1.5-320#HGM The comprehensive performance of 3 SSP is excellent. In order to further improve the flame retardant performance, reduce material damage when exposed to the flame, using expandable graphite as additives. Exploring the combustion situation encountered external heat source materials and effect of expandable graphite on the mechanical properties. The results showed that the addition of expandable graphite the microstructure of the material appears large broken particles and holes, and the brittleness of the material increases, reduces their ability to resist external force. But when subjected to external heat radiation, expandable graphite thermal expansion in the material is formed on the surface protective layer, reduce the damage to the material matrix. Improved flame retardant properties materials, thermal stability and apparent activation energy density was also reduced. In addition the flue gas can be found by adding 3 wt% of expandable graphite, which can improve the flame retardancy of the composites can be very good, Without serious damage to mechanical properties of materials. According to the original hybrid polymer composite materials and subjected to thermal radiation conditions of modified hybrid polymer composite expanded graphite, were simulated using the finite element analysis software two heated internal temperature in the process were analyzed and compared. The results show that with expandable graphite material the lower temperature difference is small and the temperature rises slowly, the area at the top of the temperature rise rapidly and the lower temperature by the flame effect is small. In hybrid polymer composite roadway based slurry used in Shanxi Shuozhou Temple ditch coal mine reinforcement. The results show that the hybrid polymer composite good filling in coal rock fractures. Enhance the carrying capacity of coal, and the reaction process produces less heat, to show the safety performance of the materials are excellent.

【学位授予单位】：中国矿业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB33;TD350.4

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