基于双硅氧烷先驱体制备的氧化硅基气凝胶研究进展

doi:10.15541/jim20150223

无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1243-1253.DOI: 10.15541/jim20150223 CSTR: 32189.14.10.15541/jim20150223

基于双硅氧烷先驱体制备的氧化硅基气凝胶研究进展

何飞^1,2, 郁万军^1,2, 方旻翰^1,2, 赫晓东^1,2, 李明伟³

(哈尔滨工业大学 1. 特种环境复合材料国防科技重点实验室; 2. 复合材料与结构研究所; 3. 金属精密热加工国防科技重点实验室, 哈尔滨 150001)

收稿日期:2015-05-11 修回日期:2015-06-10 出版日期:2015-12-20 网络出版日期:2015-11-24
作者简介:何飞(1978–), 男, 副教授. E-mail: hefei@hit.edu.cn
基金资助:
特种环境复合材料技术国防科技重点实验室开放基金(9140C490208140C49003)

An Overview on Silica Aerogels Synthesized by Siloxane Co-precursors

(1. Key Laboratory of Science and Technology on Advanced Composites, Harbin Institute of Technology, Harbin 150001, China; 2. Center for Composite Materials, Harbin Institute of Technology, Harbin 150001, China; 3. Key Laboratory for Precision Hot Processing of Materials, Harbin Institute of Technology, Harbin Institute of Technology, Harbin 150001, China)

Received:2015-05-11 Revised:2015-06-10 Published:2015-12-20 Online:2015-11-24
About author:HE Fei. E-mail: hefei@hit.edu.cn
Supported by:
Key Laboratory Opening Funding of Key Laboratory of Science and Technology on Advanced Composites (9140C490208140C49003)

摘要/Abstract

摘要：

气凝胶材料具有高比表面积、高孔隙率、低密度、低热导率和高透过率等特性, 在隔热、隔声和光学等领域具有广泛的应用前景。但该类材料纤细骨架构成的多孔结构所呈现的高脆性是限制其应用的主要因素。本文依据硅氧烷先驱体含有不可水解基团数量的特征, 综述了采用全水解双先驱体、全/部分水解双先驱体和部分水解双先驱体等三类采用双硅氧烷先驱体制备气凝胶材料的研究现状, 分析了这三类气凝胶所呈现出的组织结构特征及其在力学、热学、光学和疏水性等方面的性能特点。通过对硅氧烷先驱体类型的选择和组合, 可以设计气凝胶材料的组织结构与性能, 为改善气凝胶材料的力学行为提出了新思路。

关键词: 氧化硅气凝胶, 双硅氧烷先驱体, 力学性能, 溶胶-凝胶法, 综述

Abstract:

Due to their unique features, such as high specific surface area, high porosity, low density, low thermal conductivity, and high transmittance, aerogels can be widely applied in the fields of thermal insulation, sound insulation and optics. However, aerogels usually tend to be destructive collapse, due to their porous structures constituted by slightly brittle skeletons, which is a negative factor to restrict their applications. According to the number and variety of non-hydrolytic groups in siloxane precursors, an overview of the literatures is presented on silica aerogels synthesized by three kinds of siloxane co-precursors, i.e. integral hydrolytic co-precursors, integral/partial and partial hydrolytic co-precursors. The characteristics of porous structures and properties in mechanics, thermal insulation, optics, and hydrophobicity are analyzed. It is an effective method by choosing appropriate precursors to realize the designs and improve mechanical behaviors of aerogels in respect of structures and properties.

Key words: silica aerogels, siloxane co-precursors, mechanical properties, Sol-Gel method, review

中图分类号:

TB303

何飞, 郁万军, 方旻翰, 赫晓东, 李明伟. 基于双硅氧烷先驱体制备的氧化硅基气凝胶研究进展[J]. 无机材料学报, 2015, 30(12): 1243-1253.

HE Fei, YU Wan-Jun, FANG Min-Han, HE Xiao-Dong, LI Ming-Wei. An Overview on Silica Aerogels Synthesized by Siloxane Co-precursors[J]. Journal of Inorganic Materials, 2015, 30(12): 1243-1253.

图/表 9

表1 含有不同数量不可水解有机基团的有机硅醇盐[5]

Table 1 Organic siloxane precursors containing different non-hydrolytic groups[5]

图1 超级疏水复合材料的制备流程和油水分离实验[31]

Fig. 1 Preparation and application of superhydrophobic materials[31]

图2 不同氧化硅气凝胶制备流程图[49]

Fig. 2 Flow chart illustrating the preparation of different silica aerogels[49]

图3 以MTMS和DMDMS作为双先驱体常压干燥制备出的柔性气凝胶照片[6]

Fig. 3 Digital camera image of the flexible xerogel derived from MTMS and DMDMS co-precursor system[6]

图4 MTMS+DMDMS双先驱体制备的气凝胶三点弯曲试验(a)及实验曲线(b)[54]

Fig. 4 (a) Photograph and (b) stress-strain curves of a 3-point bending test on the MTMS-DMDMS gel[54]

图5 不同类型双先驱体制备泡沫状气凝胶的流程[54]

Fig. 5 Facile synthesis of marshmallow-like gels derived from di- and tri-functional alkoxysilanes as co-precursors[54]

图6 超双疏气凝胶制备流程和反应原理示意图[55]

Fig. 6 Synthetic approach of superamphiphobic aerogels[55] (a) The synthesis for the VTMS+VMDMS marshmallow-like gel (MG1); (b) Synthetic approach for the superamphiphobic aerogels (MG2)

图7 (a)先驱体合成过程和(b)气凝胶真空干燥过程示意图[57]

Fig. 7 (a) Synthesis of the precursor and (b) procedures of vacuum-drying to obtain aerogels[57]

表2 不同先驱体制备的氧化硅基气凝胶性能参数比较

Table 2 Comparison of performance parameters of silica aerogels prepared by different precursors

Precursors	Strength/ MPa	Elastic modulus/ MPa	Density/ (g·cm^-3)	Contact angle/(°)	Thermal conductivity/ (W·m^-1·K^-1)	Thermostability /℃
TMOS	0.031,compressed, crushed^[2]	-	0.12^[2]	Hydrophilic^[2]	0.01~0.03^[2]	600^[2]
MTMS	>9 MPa, compressed 80%, recovered^[50]	0.034~0.062 ^[1]	0.04~0.1^[1]	158~164^[1]	-	257^[1]
TMOS+PTES ^a	-	-	0.15^[5]	132^[5]	-	520^[5]
TMOS+PTES^b	-	-	0.11^[5]	121^[5]	-	520^[5]
TEOS+MTMS^a	-	-	0.107^[46]	120^[5]	-	435^[46]
TEOS+PTES^a	-	-	0.33^[5]	129^[5]	-	520^[5]
TEOS +PTES^b	-	-	0.14^[5]	115^[5]	-	520^[5]
TEOS+HMDZ ^b	-	-	0.09^[7]	146^[7]	0.08^[13]	330^[7]
MTMS+ DMDMS	~0.1, compression, recovered	-	-	hydrophobicity	-	320^[6,54]
VTMS+ VMDMS	~0.07, compressed 80%, recovered	-	0.122	150, superamphiphobic	-	170^[55]
MTMS+ GPTMS	~0.17, compressed 35%, recovered	0.46	0.104	-	0.0388	-^[56]
MPTMS+ VTMS	compression, recovered	0.117	0.085	-	0.047	-^[57]

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基于双硅氧烷先驱体制备的氧化硅基气凝胶研究进展

An Overview on Silica Aerogels Synthesized by Siloxane Co-precursors

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