CN111874917A - 一种具有特殊形状的气凝胶及其制备方法 - Google Patents

一种具有特殊形状的气凝胶及其制备方法 Download PDF

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CN111874917A
CN111874917A CN202010746039.3A CN202010746039A CN111874917A CN 111874917 A CN111874917 A CN 111874917A CN 202010746039 A CN202010746039 A CN 202010746039A CN 111874917 A CN111874917 A CN 111874917A
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aerogel
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刘韶浦
马娜
姜法兴
叶佳英
占青青
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Nano Tech Co ltd
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Abstract

本发明公开了一种具有特殊形状的无机气凝胶及其制备方法，包括以下步骤：S1、将气凝胶前驱体溶液与纤维材料复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；S2、利用耐高温模具或夹具固定所述气凝胶复合毡的形状，并对其进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。本发明采用对气凝胶纤维毡进行热处理的方式制备气凝胶，与传统的制备方法相比，该方法简单且易实现，可工业化生产，且可定制化，采用该方法制备的气凝胶更有可塑性，可用于具有特殊形状的设备或部件的保温、隔热、防火，将纤维煅烧后，除去纤维表面的有机物，可增加使用条件的安全性。

Description

一种具有特殊形状的气凝胶及其制备方法
技术领域
本发明涉及保温隔热领域，尤其涉及一种具有特殊形状的气凝胶及其制备方法。
背景技术
气凝胶是一种具有纳米微孔三维网络结构的物质，具有很好的耐温和隔热性能，其常温常压下导热系数可低至0.013W/m·K，孔隙率可高达99.8％，是世界上最轻的固体，但气凝胶因其本身脆性大，难以制备出具有特殊形状或面积较大的纯气凝胶，即使能做到制备大块的纯气凝胶，也仅限于实验室样品制备，无法进行量产。
现有技术中，目前大多数采用溶胶-凝胶法制得湿凝胶，再经醇洗、改性、干燥等步骤得到气凝胶，该方法得到的二氧化硅气凝胶一般只有长方体或圆柱体两种形状，很难做出其他形状的异形件气凝胶，因为二氧化硅气凝胶本身很脆。利用现有方法制得二氧化硅气凝胶粉，如果采用粘结剂制作异形件，会明显破坏气凝胶的结构，降低比表面积，影响其物理化学性能。
发明内容
本发明的目的是针对现有技术中的不足，提供一种具有特殊形状的气凝胶及其制备方法，该制备方法可以快速、大量工业化生产纯气凝胶，同时可制备出各种形状的气凝胶。
为实现上述目的，本发明采取的技术方案是：
本发明第一方面提供一种具有特殊形状的气凝胶的制备方法，包括以下步骤：
S1、将气凝胶前驱体溶液与纤维材料复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、利用耐高温模具或夹具固定所述气凝胶复合毡的形状，并对其进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
本发明第二发明提供一种具有特殊形状的气凝胶的制备方法，包括以下步骤：
S1、将纤维材料的形状固定，并与气凝胶前驱体溶液复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、将所述气凝胶复合毡进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
优选地，S1中，所述纤维材料为2-10mm厚的片状或卷状。
优选地，S2中，所述热处理的温度为200-600℃，升温速率为2-20℃/min，且每升温50-100℃保温20-30min；降温速率为2-20℃/min。
值得注意的是，高温处理步骤的目的是去除无机纤维表面的有机物或分解有机纤维，同时还有烧结定型的作用。
优选地，还包括：S3、对所述气凝胶进行疏水改性处理。
优选地，所述疏水改性的具体过程为：采用六甲基二硅氮烷或三甲基氯硅烷进行气体接触改性。
本发明第三方面提供根据上述方法制备的具有特殊形状的气凝胶，所述气凝胶为无机气凝胶或有机-无机杂化气凝胶。
优选地，所述无机气凝胶为二氧化硅、氧化铝、氧化锆、氧化铁和氧化钛中的一种或几种。
优选地，所述气凝胶的形状为筒形、网格形、连续弯折形、回字形、球形、瓦形、半筒形、半球形、长方体壳形、立方体壳形、锥体壳形和椭圆体壳形中的一种或几种。
优选地，所述气凝胶复合毡为所述无机气凝胶与有机纤维复合物、所述无机气凝胶与无机-有机混合纤维复合物、所述有机-无机杂化气凝胶与无机纤维复合物、所述有机-无机杂化气凝胶与有机纤维复合物、所述无机气凝胶与无机纤维复合物中的一种或几种。
本发明采用以上技术方案，与现有技术相比，具有如下技术效果：
本发明采用对气凝胶纤维毡进行热处理的方式制备气凝胶，与传统的制备方法相比，该方法简单且易实现，可工业化生产，且可定制化，采用该方法制备的气凝胶更有可塑性，可用于具有特殊形状的设备或部件的保温、隔热、防火，将纤维煅烧后，除去纤维表面的有机物，可增加使用条件的安全性。
附图说明
图1为本发明实施例1中不规则半筒形二氧化硅气凝胶的示意图；
图2为本发明实施例1中不规则半筒形二氧化硅气凝胶的SEM图。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但不作为本发明的限定。
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
本发明第一方面提供一种具有特殊形状的气凝胶的制备方法，包括以下步骤：
S1、将气凝胶前驱体溶液与纤维材料复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、利用耐高温模具或夹具固定所述气凝胶复合毡的形状，并对其进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
作为一个优选实施例，S1中，所述纤维材料为2-10mm厚的片状或卷状。
模具或夹具应为耐高温的材料，例如金属板或薄片，优选透气性材料或镂空设计使热量均匀传播，能够均匀地进行热传导，使纤维复合湿凝胶受热均匀，骨架强度更好，该方法使干燥后的气凝胶复合毡具有一定的形状，放入烘箱或马弗炉进行热处理，由室温升温至200-600℃，由于增强纤维本身的热性质，在热处理温度下，纤维因受热会逐渐分解，而此时气凝胶仍然保持其三维多孔结构，最后，纤维完全分解，只留下完整的气凝胶骨架，且保持着热处理前的形状，只是表面会有10-30％的收缩，厚度几乎不变。
本发明第二方面提供一种具有特殊形状的气凝胶的制备方法，包括以下步骤：
S1、将纤维材料的形状固定，并与气凝胶前驱体溶液复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、将所述气凝胶复合毡进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
作为一个优选实施例，S2中，所述热处理的温度为200-600℃，升温速率为2-20℃/min，且每升温50-100℃保温20-30min；降温速率为2-20℃/min。
作为一个优选实施例，还包括：S3、对所述气凝胶进行疏水改性处理。所述疏水改性的具体过程为：采用六甲基二硅氮烷或三甲基氯硅烷进行气体接触改性。
本发明第三方面提供采用上述方法制备的一种具有特殊形状的气凝胶，所述气凝胶为无机气凝胶或有机-无机杂化气凝胶；所述无机气凝胶为二氧化硅、氧化铝、氧化锆、氧化铁和氧化钛中的一种或几种。
作为一个优选实施例，所述气凝胶的形状为筒形、网格形、连续弯折形、回字形、球形、瓦形、半筒形、半球形、长方体壳形、立方体壳形、锥体壳形和椭圆体壳形中的一种或几种。
作为一个优选实施例，所述气凝胶复合毡为所述无机气凝胶与有机纤维复合物、所述无机气凝胶与无机-有机混合纤维复合物、所述有机-无机杂化气凝胶与无机纤维复合物、所述有机-无机杂化气凝胶与有机纤维复合物、所述无机气凝胶与无机纤维复合物中的一种或几种。
实施例1
S1、将正硅酸乙酯、乙醇、水、乙酸和NaOH混合后的溶液与3mm预氧化丝纤维片复合，凝胶后，得到二氧化硅与预氧化丝纤维复合湿凝胶，再经过CO2超临界干燥，即得二氧化硅气凝胶复合片；
S2、将二氧化硅气凝胶复合片用金属密网固定成不规则半筒形，固定好以后放入马弗炉，设置温度为600℃，升温速率为5℃/min，每升温100℃保温30min，升温至约100℃开始有烟出现，继续升温至约350℃，烟量消失，此后继续按照预定的温度升温，约550℃二氧化硅气凝胶复合片开始发白，说明预氧化丝纤维在分解，直至升温至600℃，保温30min，然后降温，降温速率为5℃/min，降至室温后取出，得到不规则半筒形的二氧化硅气凝胶，如图1和图2所示。
S3、用三甲基氯硅烷对经步骤S2制备的二氧化硅气凝胶进行气体接触改性，必要时可对三甲基氯硅烷进行加热。
实施例2
S1、将铝醇盐、乙醇、水、乙酸混合后的溶液与3mm预氧化丝纤维片复合，凝胶后，得到氧化铝与预氧化丝纤维复合湿凝胶，再经过CO2超临界干燥，即得氧化铝气凝胶复合片；
S2、将氧化铝气凝胶复合片裁剪固定成立方体壳形，放入马弗炉，设置温度为600℃，升温速率为2℃/min，每升温100℃保温30min，升温至约100℃开始有烟出现，继续升温至约350℃，烟量消失，此后继续按照预定的温度升温，约550℃氧化铝气凝胶复合片开始发白，说明预氧化丝纤维在分解，直至升温至600℃，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到立方体壳形的氧化铝气凝胶。
S3、用六甲基二硅氮烷对经步骤S2制备的氧化铝气凝胶进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
实施例3
S1、用3-氨基丙基三乙氧基硅烷为硅源，均苯四甲酸二酐为单体，制备聚酰亚胺交联二氧化硅凝胶，与5mm厚的PE纤维片进行复合，凝胶后，得到二氧化硅与PE纤维复合湿凝胶，进行CO2超临界干燥，即得二氧化硅气凝胶复合片；
S2、将二氧化硅气凝胶复合片用密铁丝网固定成一个半筒形，放入马弗炉，设置温度为500℃，升温速率为2℃/min，每升温50℃保温20min，升温至80℃PE纤维开始软化，继续升温至约400℃，PE纤维开始分解，直至升温至500℃，保证PE纤维完全分解，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到半筒形的聚酰亚胺交联二氧化硅气凝胶。
S3、用六甲基二硅氮烷对经步骤S2制备的聚酰亚胺交联二氧化硅气凝胶进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
实施例4
S1、用3-氨基丙基三乙氧基硅烷为硅源，均苯四甲酸二酐为单体，制备聚酰亚胺交联二氧化硅凝胶，与3mm厚的陶瓷纤维片进行复合，凝胶后，得到聚酰亚胺交联二氧化硅凝胶与陶瓷纤维复合湿凝胶，进行CO2超临界干燥，即得聚酰亚胺交联二氧化硅气凝胶复合片；
S2、将聚酰亚胺交联二氧化硅气凝胶复合片放入马弗炉，设置温度为500℃，升温速率为2℃/min，每升温50℃保温20min，中间会闻到轻微烧制的味道和烟出现，直至升温至500℃，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到硬度较高的聚酰亚胺交联二氧化硅气凝胶陶瓷纤维片。
S3、用六甲基二硅氮烷对经步骤S2制备的聚酰亚胺交联二氧化硅气凝胶进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
实施例5
S1、将PE纤维片用不锈钢丝固定成锥体壳形，然后将正硅酸乙酯、乙醇、水、乙酸和NaOH混合后的溶胶溶液与2mm厚的PE纤维片进行复合，凝胶后，得到二氧化硅与PE纤维复合湿凝胶，进行CO2超临界干燥，即得二氧化硅气凝胶复合片；
S2、将二氧化硅气凝胶复合片放入马弗炉，设置温度为500℃，升温速率为2℃/min，每升温50℃保温20min，升温至80℃PE纤维开始软化，继续升温至约400℃，PE纤维开始分解，直至升温至500℃，保证PE纤维完全分解，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到具有一定强度、规整形状的锥体壳形二氧化硅气凝胶。
S3、用六甲基二硅氮烷对经步骤S2制备的二氧化硅气凝胶进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
实施例6
S1、将喷胶棉用美工刀切割固定成筒形，然后将正硅酸乙酯、乙醇、水、乙酸和NaOH混合后的溶胶溶液与4mm厚的喷胶棉进行复合，凝胶后，得到二氧化硅与喷胶棉复合湿凝胶，进行CO2超临界干燥，即得二氧化硅气凝胶复合片；
S2、将二氧化硅气凝胶复合片放入马弗炉，设置温度为600℃，升温速率为2℃/min，每升温50℃保温20min，升温至200℃开始有烟出现，继续升温至约450℃，喷胶棉开始分解，直至升温至600℃，保证喷胶棉纤维完全分解，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到筒形的二氧化硅气凝胶。
S3、用六甲基二硅氮烷对经步骤S2制备的二氧化硅气凝胶进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
实施例7
S1、将正硅酸乙酯、乙醇、水、乙酸和NaOH混合后的溶胶溶液与150mm*160mm*10mm厚的玻璃纤维进行复合，凝胶后，得到二氧化硅与玻璃纤维复合湿凝胶，进行CO2超临界干燥，即得二氧化硅气凝胶复合玻璃纤维片(重53.8g)；
S2、将二氧化硅气凝胶复合玻璃纤维片固定成半筒形，放入马弗炉，设置温度为600℃，升温速率为2℃/min，每升温50℃保温20min，中间会闻到轻微的刺鼻味道和轻微的烟出现，直至升温至600℃，保温30min，然后降温，降温速率为2℃/min，降至室温后取出，得到半筒形的二氧化硅气凝胶，煅烧后材料重52.1g，质量减少了1.7g，说明玻璃纤维表面的有机物占3％，有机物经过高温煅烧分解，另外，经高温煅烧后的气凝胶纤维片硬度增加，表明煅烧有定型的作用。
S3、用六甲基二硅氮烷对经步骤S2制备的二氧化硅气凝胶纤维片进行气体接触改性，必要时可对六甲基二硅氮烷进行加热。
以上所述仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。

Claims (10)

1.一种具有特殊形状的气凝胶的制备方法，其特征在于，包括以下步骤：
S1、将气凝胶前驱体溶液与纤维材料复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、利用耐高温模具或夹具固定所述气凝胶复合毡的形状，并对其进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
2.一种具有特殊形状的气凝胶的制备方法，其特征在于，包括以下步骤：
S1、将纤维材料的形状固定，并与气凝胶前驱体溶液复合，制得纤维复合湿凝胶，经CO2超临界干燥后，即得气凝胶复合毡；
S2、将所述气凝胶复合毡进行热处理，待无机纤维表面的有机物或有机纤维分解后，降至室温，即得具有特殊形状的气凝胶。
3.根据权利要求1所述的具有特殊形状的气凝胶的制备方法，其特征在于，S1中，所述纤维材料为2-10mm厚的片状或卷状。
4.根据权利要求1或2所述的具有特殊形状的气凝胶的制备方法，其特征在于，S2中，所述热处理的温度为200-600℃，升温速率为2-20℃/min，且每升温50-100℃保温20-30min；降温速率为2-20℃/min。
5.根据权利要求1或2所述的具有特殊形状的气凝胶的制备方法，其特征在于，还包括：S3、对所述气凝胶进行疏水改性处理。
6.根据权利要求5所述的具有特殊形状的气凝胶的制备方法，其特征在于，所述疏水改性的具体过程为：采用六甲基二硅氮烷或三甲基氯硅烷进行气体接触改性。
7.根据权利要求1-6任一项所述的方法制备的具有特殊形状的气凝胶，其特征在于，所述气凝胶为无机气凝胶或有机-无机杂化气凝胶。
8.根据权利要求7所述的具有特殊形状的气凝胶，其特征在于，所述无机气凝胶为二氧化硅、氧化铝、氧化锆、氧化铁和氧化钛中的一种或几种。
9.根据权利要求7所述的具有特殊形状的气凝胶，其特征在于，所述气凝胶的形状为筒形、网格形、连续弯折形、回字形、球形、瓦形、半筒形、半球形、长方体壳形、立方体壳形、锥体壳形和椭圆体壳形中的一种或几种。
10.根据权利要求7所述的具有特殊形状的气凝胶，其特征在于，所述气凝胶复合毡为所述无机气凝胶与有机纤维复合物、所述无机气凝胶与无机-有机混合纤维复合物、所述有机-无机杂化气凝胶与无机纤维复合物、所述有机-无机杂化气凝胶与有机纤维复合物、所述无机气凝胶与无机纤维复合物中的一种或几种。
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Application publication date: 20201103