基于晶体生长和气凝胶技术制备芳砜纶热防护纺织品

发布时间：2018-05-10 18:49

  本文选题：芳砜纶 + 氢氧化镁　； 参考：《东华大学》2017年博士论文

【摘要】：随着社会的发展,我国的冶金、消防、军事等领域对隔热耐火防护服的需求量越来越大,目前已有防护服还不具备使穿着者安全出入火场的防护能力。提高材料的隔热阻燃性能,对开发具有高热隔绝性能、耐明火性能,又具有高度灵活性和舒适性的热防护服具有决定性作用。本课题以耐高温芳砜纶(PSA)织物作为基材,采用晶体生长技术制备出PSA/SiO_2/Mg(OH)_2隔热阻燃复合材料;采用气凝胶技术分别制备了PSA/氢氧化铝气凝胶隔热阻燃复合材料、PSA/二氧化硅-氢氧化铝气凝胶隔热阻燃复合材料和PSA/氢氧化镁铝气凝胶隔热阻燃复合材料。与纯PSA相比,其隔热性能和阻燃性能均有显著提高。具体研究内容如下所述。基于晶体生长技术制备了隔热芳砜纶织物并对其性能进行了研究。在经SiO_2整理的芳砜纶上种植Mg(OH)_2晶种后进行二次生长,制备出了具有隔热阻燃性能的负载Mg(OH)_2和SiO_2的芳砜纶复合织物(PSA/SiO_2/Mg(OH)_2)。通过控制晶体生长时间、原料浓度、氧化硅粒径大小及整理液浓度等条件,可在织物表面均匀地包覆不同形貌的Mg(OH)_2层,如倒伏片状、竖立花瓣状、蜂窝状、致密排列的倒三角台状以及致密排列的倒三角锥、倒三角台夹杂有棒状等。Mg(OH)_2包覆于芳砜纶可使其初始分解温度和最大热失重分解温度有着很大的提高,尤以蜂窝状结构包覆的芳砜纶的起始分解温度最高可达451.6℃、最大热失重分解温度最高可达483.6℃。Mg(OH)_2包覆芳砜纶后可降低其导热系数和垂直燃烧损毁长度,增强其隔热性能和阻燃性能。Mg(OH)_2的形貌对复合材料的导热系数有着极其重要的影响,通过TC-3000热线法导热系数仪于25℃测试导热系数得Mg(OH)_2以致密排列的倒三角锥状、倒三角台状并夹杂有棒状的形貌包覆时导热系数最低,仅为0.0553 W/(m·K),蜂窝状形貌包覆时导热系数可低至0.0559 W/(m·K),致密排列的倒三角台形貌包覆时低至0.0568 W/(m·K),远低于芳砜纶原布的0.0975W/(m·K)。PSA/SiO_2/Mg(OH)_2复合材料具有优异的阻燃性能,损毁长度为1.20 cm,属于难燃材料。多孔结构有利于提高材料的隔热性能,为了进一步提高芳砜纶织物的隔热性能,采用溶胶-凝胶法和常压干燥法制得了氢氧化铝气凝胶并将其成功地应用到芳砜纶上。氢氧化铝气凝胶的孔结构和表观密度对其隔热性能均有影响,孔容越大、表观密度越低,复合材料的导热系数越低、隔热性能越好。通过改变反应配比来调控气凝胶的孔结构和表观密度,获得了表观密度为0.172~0.645 g/cm3、孔容为0.717~2.325 cm3/g、比表面积为292.703~408.696 m2/g、平均孔径为10.9~21.8 nm的白色半透明块状氢氧化铝气凝胶,其为γ-Al OOH勃姆石晶体,空间网络结构由纳米纤维状颗粒相互交错连接而成。采用溶胶-凝胶成型法和常压干燥法制得了PSA/氢氧化铝气凝胶复合材料,通过TC-3000热线法导热系数仪于25℃测试导热系数、垂直燃烧仪测试损毁长度表征了其隔热阻燃性能,其与芳砜纶原织物相比,导热系数从0.0975 W/(m·K)降到0.0599 W/(m·K),损毁长度从4.90 cm减少到1.25 cm,隔热和阻燃性能得到显著提高。为进一步降低氢氧化铝气凝胶的表观密度、增大其孔容,在其制备过程中加入正硅酸四乙酯(TEOS),获得了表观密度为0.140g/cm3,比表面积为366.686 m2/g,孔容为2.798 cm3/g,平均孔径为28.3 nm的白色半透明块状二氧化硅-氢氧化铝复合气凝胶,其为γ-Al OOH勃姆石晶体与非晶态SiO_2的混合物,空间网络结构由纳米叶片状颗粒彼此相互交错连接而成。采用溶胶-凝胶成型法和常压干燥法成功地制得了PSA/二氧化硅-氢氧化铝气凝胶复合材料,通过TC-3000热线法导热系数仪于25℃测试导热系数和垂直燃烧仪测试损毁长度表征了其隔热阻燃性能,与芳砜纶原织物相比,其导热系数从0.0975 W/(m·K)降到0.0581 W/(m·K),垂直燃烧损毁长度从4.90 cm减少到2.85 cm,隔热和阻燃性能得到了较大提高。为进一步提高氢氧化铝气凝胶的隔热性能,采用溶胶-凝胶法和常压干燥、真空干燥相结合的方法制得了白色氢氧化镁铝气凝胶。通过改变反应配比来调控氢氧化镁铝气凝胶的物相组成、表观密度和孔结构,获得了表观密度为0.108~0.689 g/cm3,孔容为0.655~2.430 cm3/g,比表面积为177.514~459.376 m2/g,平均孔径为5.1~32.4 nm的具有不同物相组成的氢氧化镁铝气凝胶。其空间网络结构由纳米片状颗粒相互交错连接而成,或由片状氢氧化镁铝相互交错叠加构成的球形花朵状颗粒相互连接堆积而成。采用溶胶-凝胶成型法和常压干燥、真空干燥相结合的方法成功地制得了PSA/氢氧化镁铝气凝胶复合材料。通过TC-3000热线法导热系数仪于25℃测试导热系数和垂直燃烧仪测试损毁长度表征了其隔热阻燃性能,与芳砜纶原织物相比,其导热系数从0.0975 W/(m·K)降到0.0532W/(m·K),垂直燃烧损毁长度从4.90 cm减少到2.10 cm,隔热和阻燃性能都得到了显著提高。对比PSA/SiO_2/Mg(OH)_2复合材料、PSA/氢氧化铝气凝胶复合材料、PSA/二氧化硅-氢氧化铝气凝胶复合材料、PSA/氢氧化镁铝气凝胶复合材料的隔热阻燃性能可知,PSA/氢氧化镁铝气凝胶复合材料的隔热性能最好,导热系数可低至0.0532 W/(m·K);倒三角台形貌Mg(OH)_2包覆的PSA/SiO_2/Mg(OH)_2复合材料的阻燃性能最好,垂直燃烧损毁长度可低至1.20 cm。本文的研究结果可为具有高隔热性能和高耐火性能的热防护纺织品的开发提供参考。
[Abstract]:With the development of society, the demand for heat insulation fire-resistant protective clothing is becoming more and more large in our metallurgical, fire, military and other fields. At present, the protective clothing has not been able to protect the wearer from the safety of the fire field. It improves the heat insulation and flame retardancy of the material, and has high thermal insulation and bright fire resistance, and has high flexibility and flexibility. The thermal protective clothing of comfort has a decisive effect. The heat resistant and Flame Retardant Composites of PSA/SiO_2/Mg (OH) _2 are prepared by crystal growth technology with high temperature resistant polysulfone (PSA) fabric as the substrate, and the heat insulation and Flame Retardant Composites of PSA/ hydrogel aerogel are prepared by aerogel technology, and the PSA/ silica - aluminum hydroxide gas condensate is prepared. The thermal insulation and flame retardancy of PSA/ magnesium hydroxide aluminum aerogel have been improved significantly compared with pure PSA. The specific research contents are as follows. The thermal insulation polysulfone fabric is prepared based on the crystal growth technology and its properties are studied. The SiO_2 finishing polysulfone fiber is used. After planting Mg (OH) _2 seeds for two times, the polysulfonamide composite fabric (PSA/SiO_2/Mg (OH) _2) with Mg (OH) _2 and SiO_2 with heat insulation and flame retardancy was prepared. By controlling the growth time of the crystal, the concentration of the raw material, the size of the silicon oxide particle and the concentration of the finishing liquid, the Mg (OH) layer with different morphologies could be coated evenly on the surface of the fabric. Such as lodging flake, petal shaped, honeycomb, dense arranged inverted triangulation and dense arranged inverted triangle cone,.Mg (OH) _2 coated with polysulfonamide in the inverted triangle can make the initial decomposition temperature and maximum thermal weight loss decomposition temperature be greatly improved, especially the initial decomposition temperature of the polysulfone coated by honeycomb structure. The maximum thermal loss decomposition temperature is up to 451.6 degrees C, the maximum thermal weight loss decomposition temperature can be up to 483.6.Mg (OH) _2 coated with polysulfone fiber. The thermal conductivity and the vertical combustion damage length can be reduced, and the thermal insulation and flame retardant properties of.Mg (OH) _2 have been greatly influenced by the thermal conductivity of the composites by the TC-3000 hot wire thermal conductivity meter. The thermal conductivity of Mg (OH) _2 is measured at 25 C, and the thermal conductivity is the lowest when the inverted triangulation and clad is clad with a rod like appearance, only 0.0553 W/ (M. K). The thermal conductivity of the honeycomb shape coating can be as low as 0.0559 W/ (M. K), and the dense arrangement of the inverted triangle is as low as 0.0568 W/ (m K), far below it. The 0.0975W/ (M. K).PSA/SiO_2/Mg (OH) _2 composite has excellent flame retardancy and the damage length is 1.20 cm, which is a refractory material. The porous structure helps to improve the insulation property of the material. In order to further improve the heat insulation property of the polysulfone fabric, the sol-gel method and the atmospheric drying method are used to obtain the aluminum hydroxide gas. The pore structure and apparent density of the aluminum hydroxide aerogels have influence on the thermal insulation properties of the hydrogel. The larger the pore volume, the lower the apparent density, the lower the thermal conductivity of the composite, the better the heat insulation performance. The apparent density is obtained by changing the reaction ratio to regulate the pore structure and apparent density of the aerogels. The degree is 0.172~0.645 g/cm3, Kong Rong is 0.717~2.325 cm3/g, the specific surface area is 292.703~408.696 m2/g, the average pore size is 10.9~21.8 nm, the white semitransparent massive aluminum hydroxide aerogel is the gamma -Al OOH boehmite crystal. The space network structure is interlaced with the nanofibrous particles. The sol-gel forming method and the atmospheric pressure dry method are used. The PSA/ aluminum hydroxide aerogel composite was obtained by dryness. The thermal conductivity was measured by the TC-3000 hot wire thermal conductivity meter at 25 C. The damage length of the vertical combustion instrument was tested for its thermal insulation and flame retardancy. Compared with the aramid fabric, the thermal conductivity decreased from 0.0975 W/ (M. K) to 0.0599 W/ (M. K), and the damage length was reduced from 4.90 cm to 1.25. Cm, in order to further reduce the apparent density of the aluminum hydroxide aerogel and increase its Kong Rong, four ethyl orthosilicate (TEOS) is added to the preparation process. The apparent density is 0.140g/cm3, the surface area is 366.686 m2/g, the Kong Rong is 2.798 cm3/g, and the average pore size is 28.3 nm white semitransparent block. The silica - aluminum hydroxide compound aerogel is a mixture of gamma -Al OOH boehmite crystal and amorphous SiO_2. The spatial network structure is interlaced with each other. The PSA/ two silicon oxide - aluminum hydroxide aerogel composite is successfully prepared by sol-gel method and atmospheric pressure drying method, through TC-3 The thermal conductivity of the 000 hot wire method was measured at 25 degrees centigrade thermal conductivity and the test damage length of the vertical combustion instrument. Compared with the aramid fabric, the thermal conductivity decreased from 0.0975 W/ (m K) to 0.0581 W/ (M. K), and the vertical combustion damage length decreased from 4.90 cm to 2.85 cm, and the heat insulation and flame retardant properties were greatly improved. In order to further improve the insulation performance of aluminum hydroxide aerogels, white magnesium aluminum hydroxide aerogels were prepared by combining sol-gel method with atmospheric pressure drying and vacuum drying. By changing the reaction ratio, the phase composition, apparent density and pore structure of magnesium hydroxide aerogels were controlled, and the apparent density of 0.108~0.689 g/ was obtained. Cm3, Kong Rong is a 0.655~2.430 cm3/g, with a specific surface area of 177.514~459.376 m2/g and an average pore size of 5.1~32.4 nm, with different phases of magnesium aluminum hydroxide. The spatial network structure is interlaced by interlaced nanometallic particles, or the spherical flower particles composed of flake magnesium aluminum phase interlaced and interlaced with each other. PSA/ magnesium aluminium aerogel composite was successfully prepared by combination of sol-gel forming method, atmospheric drying and vacuum drying. The thermal conductivity and damage length of vertical combustion apparatus were tested by TC-3000 hot wire thermal conductivity meter at 25 C. The thermal conductivity decreased from 0.0975 W/ (M. K) to 0.0532W/ (M. K), the vertical combustion damage length decreased from 4.90 cm to 2.10 cm, and the heat insulation and flame retardant properties were greatly improved. The heat insulation and flame retardancy of the magnesium aluminum aerogel composite can be found that the heat insulation performance of PSA/ mg Al aerogel composite material is the best, the thermal conductivity can be as low as 0.0532 W/ (M. K), and the Mg (OH) _2 coated PSA/SiO_2/Mg (OH) _2 composite with Mg (OH) _2 has the best flame retardancy and the vertical combustion damage length can be lower to 1.20 cm.. The results can provide references for the development of thermal protective textiles with high thermal insulation and high fire resistance.

【学位授予单位】：东华大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TS106;TS941.731
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本文编号：1870455