气凝胶骨架结构的有机-无机交联度对其力学、热学性能的影响

doi:10.15541/jim20190186

无机材料学报 ›› 2020, Vol. 35 ›› Issue (4): 454-460.DOI: 10.15541/jim20190186

所属专题：结构陶瓷论文精选(二)；【虚拟专辑】气凝胶，玻璃(2020~2021)

气凝胶骨架结构的有机-无机交联度对其力学、热学性能的影响

张泽,王晓栋(),沈军()

同济大学物理科学与工程学院, 上海市特殊人工微结构材料与技术重点实验室, 上海 200092

收稿日期:2019-04-29 修回日期:2019-07-16 出版日期:2020-04-20 网络出版日期:2019-09-04
作者简介:张泽(1994-), 男, 博士研究生. E-mail: 1195705952@qq.com
基金资助:
国家重点研发计划“纳米科技”重点专项项目(2017YFA0204600);国家自然科学基金(11874288)

Effect of Organic-inorganic Crosslinking Degree on the Mechanical and Thermal Properties of Aerogels

ZHANG Ze,WANG Xiaodong(),SHEN Jun()

Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, School of Physics Science and Engineering, Tongji University, Shanghai 200092, China

Received:2019-04-29 Revised:2019-07-16 Published:2020-04-20 Online:2019-09-04
Supported by:
National Key Research and Development Program of China(2017YFA0204600);National Natural Science Foundation of China(11874288)

摘要/Abstract

摘要：

硅系气凝胶是目前研究理论最为完善、合成技术最为成熟的气凝胶材料。本工作分别以四乙氧基硅烷(TEOS)、甲基三甲氧基硅烷(MTMS)、MTMS与二甲基二甲氧基硅烷(DMDMS)混合硅源、乙烯基甲基二甲氧基硅烷(VMDMS)为前驱体, 制备了不同种类的硅系气凝胶。所制得的硅系气凝胶具有较高的比表面积, 并呈现出纳米多孔的网络结构。本研究详细探讨了前驱体结构对气凝胶的力学及热学性能的影响。结果表明, 硅系气凝胶的骨架结构交联度越低, 弹性性能越好; 同时, 引入有机碳氢链会进一步提升气凝胶的弹性性能。所制备的硅系气凝胶兼具良好的保温隔热性能, 常温热导率在0.032~0.041 W/(m·K)范围内, 热重损失随着骨架结构内有机组分的增多而增大。这些优良的力学及热学性能使硅系气凝胶在保温隔热、储能等领域均具有广阔的应用前景。

关键词: 气凝胶, 骨架结构, 力学性能, 热学性能

Abstract:

In all kinds of aerogels, silicon-based aerogel possesses the most comprehensive mechanism of Sol-Gel process and maturest synthesis process. In this work, different types of silicon-based aerogels were prepared via different silicon precursors including tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), vinylmethyldimethoxysilane (VMDMS) and the mixed precursor of MTMS and dimethyldimethoxysilane (DMDMS). All samples display high specific surface area and porous microstructure. Effect of the precursor structure on the mechanical and thermal properties of final samples was deeply investigated. The results show that elastic property of silicon-based aerogels depends greatly on the crosslinking degree of their skeleton. The lower the crosslinking degree of the sample is, the better the elastic property is. Furthermore, the elastic property can be further improved by introducing hydrocarbon chains into the skeleton. Thermal conductivity of the obtained aerogels is between 0.032 and 0.041 W/(m·K) at room temperature. Their weight loss increases with the increase of the organic component in the skeleton. Superior mechanical and thermal properties enable silicon-based aerogels to be promising candidates for thermal insulation and energy storage.

Key words: aerogel, skeleton structure, mechanical property, thermal property

中图分类号:

O648

张泽,王晓栋,沈军. 气凝胶骨架结构的有机-无机交联度对其力学、热学性能的影响[J]. 无机材料学报, 2020, 35(4): 454-460.

ZHANG Ze,WANG Xiaodong,SHEN Jun. Effect of Organic-inorganic Crosslinking Degree on the Mechanical and Thermal Properties of Aerogels[J]. Journal of Inorganic Materials, 2020, 35(4): 454-460.

图/表 9

图1 硅系气凝胶的实物照片(样品1~4)

Fig. 1 Photograph of silicon-based aerogels Samples 1-4 are from left to right in sequence

表1 硅系气凝胶的部分物理性能

Table 1 Physical properties of silicon-based aerogels

Sample	ρ^a/(g·cm^-3)	S_BET^b/(m²·g^-1)	d^c/nm	ε^d/(cm³·g^-1)	λ^e/(W·m^-1·K^-1)	R^f/%	Y^g/MPa
1	0.194	843	20.22	4.900	0.036	10%	0.71
2	0.192	1165	18.23	3.600	0.034	20%	0.82
3	0.156	34	1.72	0.025	0.041	27%	9.54×10^-3
4	0.188	1403	16.31	3.700	0.032	100%	4.51

图2 硅系气凝胶的SEM照片

Fig. 2 SEM images of silicon-based aerogels (a-d) represent samples 1-4, respectively

图3 硅系气凝胶的N2吸附-脱附等温线(a~b)和孔径分布图(c~d)

Fig. 3 N2 adsorption/desorption isotherms (a-b) and BJH pore size distribution (c-d) of silicon-based aerogels

图4 硅系气凝胶的红外谱图

Fig. 4 FT-IR spectra of silicon-based aerogels

图5 硅系气凝胶的骨架结构

Fig. 5 Skeleton structure of 4 silicon-based aerogels obtained from (a) TEOS, (b) MTMS, (c) mixed precursor of MTMS and DMDMS, and (d) VMDMS

图6 硅系气凝胶的29Si MAS NMR谱图

Fig. 6 29Si MAS NMR spectra of silicon-based aerogels

图7 硅系气凝胶的TG曲线

Fig. 7 TG curves of silicon-based aerogels

图8 硅系气凝胶的应力应变曲线图

Fig. 8 Stress-strain curves of silicon-based aerogels (a) Sample 1, (b) Sample 2, (c) Sample 3, (d) Sample 4. Insets in (a-d) show the skeleton structure of corresponding aerogels

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气凝胶骨架结构的有机-无机交联度对其力学、热学性能的影响

Effect of Organic-inorganic Crosslinking Degree on the Mechanical and Thermal Properties of Aerogels

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