CN108328620A - 疏水型发泡水泥复合硅气凝胶材料的制备方法 - Google Patents
疏水型发泡水泥复合硅气凝胶材料的制备方法 Download PDFInfo
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Abstract
本发明属于纳米多孔材料的制备工艺领域,尤其涉及一种疏水型发泡水泥复合硅气凝胶材料的制备方法。以正硅酸乙酯为前驱体,有机硅烷为改性剂,发泡水泥为硬质增强基体,采用溶胶‑凝胶法,原位聚合法以及真空浸渍工艺,并结合快速乙醇超临界干燥制备而成。制得的疏水型发泡水泥复合硅气凝胶材料密度为0.40‑0.73g/cm3,抗压强度为0.8‑2.1MPa,常温热导率为0.054‑0.186W·m‑1·K‑1,疏水角为118°‑146°。该工艺用料低廉,制备方法简捷,生产周期由传统方法的5‑7天压缩至10h以内,在缩短制备周期的同时还节省了大量乙醇,具备大规模工业化生产意义。
Description
技术领域
本发明属于纳米多孔材料的制备工艺领域,涉及一种耐高温,低热导率,疏水性好及高强度的疏水型发泡水泥复合硅气凝胶材料的制备方法。
背景技术
SiO2气凝胶是具有纳米多孔网络结构的固体材料。作为迄今为止绝热性能最好的材料,SiO2气凝胶具有高比表面积、高孔隙率、低密度和低热导率等优异性能,在航空航天、建筑、化工等领域作为保温、隔热材料具有较为广阔的应用前景。但是二氧化硅气凝胶脆性大、强度低,制约了其作为隔热材料在很多领域的工程化应用。而且常规方法制备的SiO2气凝胶表面都含有一定的亲水性基团硅羟基,在高温潮湿环境下使用时易吸潮后造成孔结构收缩和骨架坍塌,从而导致其隔热效果下降及使用寿命缩短。
目前,玻璃纤维作为一种低成本增强相被广泛应用于气凝胶产业化,但其柔软、易弯曲的特性无法承受剪切应力,不适宜作为承重结构直接使用。而且在潮湿环境中,气凝胶组分性能有所降低。
发泡水泥因其廉价、质轻的特性被应用于建筑保温领域,但其热导率相对较高、使用温度低导致其无法在高温热工设备中得到使用。
发明内容
本发明的目的是为了改进现有技术的不足而提供一种疏水型发泡水泥复合硅气凝胶材料的制备方法。
本发明的技术方案为:使用发泡水泥作为基体,疏水性硅气凝胶均匀填充在其孔洞中,在避免了因气凝胶亲水性导致其孔结构破坏的同时,提高了气凝胶材料的机械强度,使其具备抗压抗折能力,并且根据使用环境要求的不同可进行后期机械加工,有一定承重能力,可作为特定部位的结构材料使用。其中疏水改性二氧化硅气凝胶组分采用快速制备法,将时间从5-7天缩短至10h以内,省去了凝胶、溶剂置换和老化过程,节省大量乙醇溶剂的用量同时也大大缩短了制备时间。
本发明的具体技术方案为:一种疏水型发泡水泥复合硅气凝胶材料的制备方法,其具体步骤如下:
(1)溶胶的制备
将前驱体与原位改性剂、水和乙醇按一定比例混合并加入容器搅拌一段时间,通过加入碱试剂调节pH值,得到疏水性硅溶胶;
(2)与发泡水泥基体的复合
将硬质发泡水泥材料放在容器(或者模具)中,将步骤(1)制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准,使用真空干燥箱进行真空浸渍复合发泡水泥,抽真空2-3次并及时添加溶胶,使发泡水泥基体得到充分浸润,得到发泡水泥增强疏水SiO2溶胶;此过程之后省去了凝胶和老化过程,直接进行干燥;
(3)乙醇超临界干燥
将步骤(2)得到的发泡水泥增强疏水SiO2溶胶连带容器放入超临界反应釜中,干燥介质为乙醇,气氛为氮气,干燥温度为250℃~290℃,压力为8~12MPa,恒温恒压状态下维持2-4个小时,放出气体后待反应釜温度降温(一般至室温)后即得到疏水型发泡水泥复合硅气凝胶材料。
优选步骤(1)中所使用的前驱体原料为正硅酸四乙酯(TEOS),原位改性剂为甲基三乙氧基硅烷(MTES)、苯基三乙氧基硅烷(PTES)或乙烯基三乙氧基硅烷(VTES)中的一种。
优选步骤(1)中前驱体、水、乙醇、原位改性剂按1:(0.14~0.28):(3.12~4.17):(0.17~0.53)的体积比进行配制。
优选步骤(1)中搅拌时间在0.5-2h之间。
优选步骤(1)中所使用的碱性试剂为NH3.H2O浓度在8-13mol/L之间的氨水溶液。
优选步骤(1)中pH值为7.0~9.0。
优选步骤(2)中硬质发泡水泥材料的密度为0.32~0.68g/cm3,常温热导率在0.098~0.210W·m-1·K-1之间。
优选步骤(2)中所述的真空干燥箱温度设置为20℃~40℃,真空度设置为10~30KPa。
本发明所制得的疏水型发泡水泥复合硅气凝胶材料的密度为0.40-0.73g/cm3,抗压强度为0.8-2.1MPa,常温热导率为0.054-0.186W·m-1·K-1,疏水角为118°-146°。
本发明采用原位聚合法对气凝胶进行疏水改性并与硬质发泡水泥复合,制得疏水性好、高强度、低热导的疏水型发泡水泥复合硅气凝胶材料,同时采用快速制备法,将制备周期从5-7天缩短至10h以内。所制备的复合材料既能起到良好的疏水隔热效果又能在某些特定结构中承受一定的重力。
有益效果:
(1)相比较于传统的玻璃纤维增强SiO2气凝胶样品,本发明制备得到的疏水型发泡水泥复合硅气凝胶样品力学性能优异、具备一定抗压强度,可用于结构材料直接承重。
(2)相比较于发泡水泥,硅钙板等硬质隔热材料,本发明所制备得疏水型发泡水泥复合硅气凝胶材料具有更好得隔热性能,热导率更低。
(3)相比较于传统的复合气凝胶制品,本发明在保证产品性能的基础上采用原位聚合法对气凝胶进行疏水改性,避免了因气凝胶亲水性而导致其孔结构的破坏。
(4)相比较于传统的复合气凝胶制品,本发明采用快速制备法省去了凝胶、溶剂置换和老化过程,将时间从5-7天缩短至10h以内,极大提高了效率,适合工业化生产。
附图说明
图1是实例1中所制备的疏水型发泡水泥复合硅气凝胶材料的扫描电子显微镜照片。
图2是实例2中所制备的疏水型发泡水泥复合硅气凝胶材料的傅里叶红外光谱分析图。
图3是实例2中所制备的疏水型发泡水泥复合硅气凝胶材料的接触角测试图。
图4是实例3中所制备样品的热失重-差热分析图。
具体实施方式
下面结合实例对本发明作进一步说明,但保护范围并不限于此。
实例1
在烧杯中加入44.7ml正硅酸四乙酯,12.5ml去离子水,186.3ml乙醇与20mlMTES,将混合溶液搅拌1h30min后,逐滴加入8mol/L的氨水溶液,调节溶液pH至8后搅拌均匀。将密度为0.47g/cm3,常温热导率为0.152W·m-1·K-1硬质发泡水泥材料放在模具中,将刚制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准。使用真空干燥箱进行真空浸渍复合发发泡水泥,真空干燥箱温度设置为20℃,真空度设置为10KPa。抽真空2次并及时添加溶胶,使发泡水泥基体得到充分浸润。无需等待其凝胶,直接将样品连带容器放入反应釜中进行乙醇超临界干燥,干燥温度设置为270℃,温度升上去之后,压力维持在10MPa,恒温恒压状态下维持3h,然后保持匀速在30min内将气体放出,等反应釜温度降下之后取出容器,将水泥基体外部的气凝胶剥掉后得到疏水型发泡水泥复合硅气凝胶材料。所制备材料密度为0.52g/cm3,抗压强度为1.5MPa,常温热导率为0.122W·m-1·K-1,疏水角为134°。
图1为疏水型发泡水泥复合硅气凝胶材料的扫描电子显微镜照片,气凝胶组分均匀且充分填充于基体的孔结构之中,且保持三维纳米多孔的特征结构,通过限制了空气分子热运动提高了材料的隔热性能。
实例2
在烧杯中加入53.7ml正硅酸四乙酯,9.7ml去离子水,183.7ml乙醇与19.9mlMTES,将混合溶液搅拌1h后,逐滴加入9mol/L的氨水溶液,调节溶液pH至8后搅拌均匀。将密度为0.52g/cm3,常温热导率为0.183W·m-1·K-1的硬质发泡水泥材料放在模具中,将刚制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准。使用真空干燥箱进行真空浸渍复合发泡水泥,真空干燥箱温度设置为40℃,真空度设置为30KPa。抽真空3次并及时添加溶胶,使发泡水泥基体得到充分浸润。无需等待其凝胶,直接将样品连带容器放入反应釜中进行乙醇超临界干燥,干燥温度设置为260℃,温度升上去之后,压力维持在9MPa,恒温恒压状态下维持2.5h,然后保持匀速在25min内将气体放出,等反应釜温度降下之后取出容器,将水泥基体外部的气凝胶剥掉后得到疏水型发泡水泥复合硅气凝胶材料。所制备材料密度为0.6g/cm3,抗压强度为1.8MPa,常温热导率为0.152W·m-1·K-1,疏水角为128.1°。
图2和图3分别为所制备的发泡水泥复合SiO2气凝胶材料的红外光谱和接触角测试图像,在2980cm-1附近出现了较强的甲基伸缩振动峰,同时128.1°的接触角表明材料具有良好的疏水性能。
实例3
在烧杯中加入39.3ml正硅酸四乙酯,11.0ml去离子水,163.8ml乙醇与20.8mlMTES,将混合溶液搅拌2h后,逐滴加入13mol/L的氨水溶液,调节溶液pH至9后搅拌均匀。将密度为0.32g/cm3,常温热导率为0.098W·m-1·K-1的硬质发泡水泥材料放在模具中,将刚制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准。使用真空干燥箱进行真空浸渍复合发泡水泥,真空干燥箱温度设置为30℃,真空度设置为20KPa。抽真空2次并及时添加溶胶,使发泡水泥基体得到充分浸润。无需等待其凝胶,直接将样品连带容器放入反应釜中进行乙醇超临界干燥,干燥温度设置为290℃,温度升上去之后,压力维持在12MPa,恒温恒压状态下维持4h,然后保持匀速在40min内将气体放出,等反应釜温度降下之后取出容器,将水泥基体外部的气凝胶剥掉后得到疏水型发泡水泥复合硅气凝胶材料。所制备材料密度为0.40g/cm3,抗压强度为0.8MPa,常温热导率为0.054W·m-1·K-1,疏水角为146°。
图4为所制备材料的热重-比热分析,30-100℃的阶段性失重是由于吸附水和乙醇蒸发导致的,而在280℃伴随着质量下降,出现气凝胶表面基团氧化的特征吸热峰,该材料在1000℃内热失重不到15%,热稳定性良好。
实例4
在烧杯中加入58.2ml正硅酸四乙酯,8.2ml去离子水,181.6ml乙醇与9.9ml MTES,将混合溶液搅拌0.5h后,逐滴加入8mol/L的氨水溶液,调节溶液pH至8后搅拌均匀,将密度为0.68g/cm3,常温热导率为0.210W·m-1·K-1的硬质发泡水泥材料放在模具中,将刚制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准。使用真空干燥箱进行真空浸渍复合发泡水泥,真空干燥箱温度设置为25℃,真空度设置为15KPa。抽真空3次并及时添加溶胶,使发泡水泥基体得到充分浸润。无需等待其凝胶,直接将样品连带容器放入反应釜中进行乙醇超临界干燥,干燥温度设置为250℃,温度升上去之后,压力维持在8MPa,恒温恒压状态下维持2h,然后保持匀速在20min内将气体放出,等反应釜温度降下之后取出容器,将水泥基体外部的气凝胶剥掉后得到疏水型发泡水泥复合硅气凝胶材料。所制备材料密度为0.73g/cm3,抗压强度为2.1MPa,常温热导率为0.186W·m-1·K-1,疏水角为118°。
实例5
在烧杯中加入42.5ml正硅酸四乙酯,9.8ml去离子水,159.4ml乙醇与20.4mlMTES,将混合溶液搅拌1.5h后,逐滴加入10mol/L的氨水溶液,调节溶液pH至9后搅拌均匀。将密度为0.41g/cm3,常温热导率为0.114W·m-1·K-1的硬质发泡水泥材料放在模具中,将刚制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准。使用真空干燥箱进行真空浸渍复合发泡水泥,真空干燥箱温度设置为35℃,真空度设置为25KPa。抽真空2次并及时添加溶胶,使发泡水泥基体得到充分浸润。无需等待其凝胶,直接将样品连带容器放入反应釜中进行乙醇超临界干燥,干燥温度设置为280℃,温度升上去之后,压力维持在11MPa,恒温恒压状态下维持3.5h,然后保持匀速在35min内将气体放出,等反应釜温度降下之后取出容器,将水泥基体外部的气凝胶剥掉后得到疏水型发泡水泥复合硅气凝胶材料。所制备材料密度为0.46g/cm3,抗压强度为1.2MPa,常温热导率为0.083W·m-1·K-1,疏水角为141°。
Claims (9)
1.一种疏水型发泡水泥复合硅气凝胶材料的制备方法,其具体步骤如下:
(1)溶胶的制备
将前驱体与原位改性剂、水和乙醇按一定比例混合并加入容器搅拌一段时间,通过加入碱试剂调节pH值,得到疏水性硅溶胶;
(2)与发泡水泥基体的复合
将硬质发泡水泥材料放在容器中,将步骤(1)制得的疏水性硅溶胶倾倒入容器中,以没过基体材料为准,使用真空干燥箱进行真空浸渍复合发泡水泥,抽真空2-3次并及时添加溶胶,使发泡水泥基体得到充分浸润,得到发泡水泥增强疏水SiO2溶胶;
(3)乙醇超临界干燥
将步骤(2)得到的发泡水泥增强疏水SiO2溶胶连带容器放入超临界反应釜中,干燥介质为乙醇,气氛为氮气,干燥温度为250℃~290℃,压力为8~12MPa,恒温恒压状态下维持2-4个小时,放出气体后待反应釜温度降温后即得到疏水型发泡水泥复合硅气凝胶材料。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中所使用的前驱体原料为正硅酸四乙酯,原位改性剂为甲基三乙氧基硅烷、苯基三乙氧基硅烷或乙烯基三乙氧基硅烷中的一种。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中前驱体、水、乙醇、原位改性剂按1:(0.14~0.28):(3.12~4.17):(0.17~0.53)的体积比进行配制。
4.根据权利要求1所述的制备方法,其特征在于步骤(1)中搅拌时间在0.5-2h之间。
5.根据权利要求1所述的制备方法,其特征在于步骤(1)中所使用的碱性试剂为碱性试剂为NH3.H2O浓度在8-13mol/L之间的氨水溶液。
6.根据权利要求1所述的制备方法,其特征在于步骤(1)中pH值为7.0~9.0。
7.根据权利要求1所述的制备方法,其特征在于步骤(2)中硬质发泡水泥材料的密度为0.32~0.68g/cm3,常温热导率在0.098~0.210W·m-1·K-1之间。
8.根据权利要求1所述的制备方法,其特征在于步骤(2)中所述的真空干燥箱温度设置为20℃~40℃,真空度设置为10~30KPa。
9.根据权利要求1所述的制备方法,其特征在于制得的疏水型发泡水泥复合硅气凝胶材料的密度为0.40-0.73g/cm3,抗压强度为0.8-2.1MPa,常温热导率为0.054-0.186W·m-1·K-1,疏水角为118°-146°。
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