纺织学报 ›› 2023, Vol. 44 ›› Issue (08): 217-224.doi: 10.13475/j.fzxb.20220307302

• 综合述评 • 上一篇    下一篇

柔性增强二氧化硅气凝胶的研究进展

吕红丽1, 罗丽娟2, 师建军2, 郑振荣1(), 李红晨1   

  1. 1.天津工业大学 纺织科学与工程学院, 天津 300387
    2.航天材料及工艺研究所, 北京 100076
  • 收稿日期:2022-03-21 修回日期:2022-05-28 出版日期:2023-08-15 发布日期:2023-09-21
  • 通讯作者: 郑振荣(1981—),女,教授,博士。主要研究方向为柔性防热材料的制备与性能研究。E-mail: tianjinzhengzr@163.com
  • 作者简介:吕红丽(1997—),女,硕士生。主要研究方向为二氧化硅气凝胶的制备及性能研究。
  • 基金资助:
    国家自然科学基金项目(52003071)

Research progress in flexible reinforced silica aerogels

LÜ Hongli1, LUO Lijuan2, SHI Jianjun2, ZHENG Zhenrong1(), LI Hongchen1   

  1. 1. School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
    2. Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China
  • Received:2022-03-21 Revised:2022-05-28 Published:2023-08-15 Online:2023-09-21

摘要:

传统二氧化硅气凝胶隔热性能优异、制备工艺成熟,但固有的脆性严重限制了其推广使用。阐述了近年来硅气凝胶柔性增强方面的研究进展,通过详细分析现有柔性增强研究中存在的问题,提出组分增强时要通过适当选择硅烷前驱体,并将其与有机聚合物或纤维复合来构建柔性网络骨架,实现化学结构和网络骨架的调控;在工艺优化方面,详细介绍了仿生干燥技术和3D打印技术2种新工艺。最后,根据柔性气凝胶的未来发展方向,对突破常压干燥技术、开展聚合物交联或纳米纤维增强制备结构有序可控的柔性复合气凝胶进行了展望。

关键词: 柔性增强, 二氧化硅气凝胶, 隔热材料, 聚合物交联, 结构可控

Abstract:

Significance Silica aerogel is known as a super thermal insulation material due to its low density, high porosity, low thermal conductivity and strong design. It can be made into powder, microspheres, films and other forms of materials. These excellent properties make it widely used in heat insulation, adsorption, electromagnetic shielding, photocatalysis and other fields. The traditional silica aerogel preparation process is mature, but its network skeleton is slender and fragile offering poor mechanical properties, which seriously limits its applications. The research methods and the strategy for achieving flexible enhancement of silica aerogels are systematically reviewed, including the preparation process and material properties of different silica aerogels, aiming to establish thorough understanding of the design, preparation and applications of flexible aerogel materials for future development.

Progress Silica aerogels prepared by simple hydrophobic modification have slender skeleton and poor mechanical properties, which limits the allocation. At present, the flexible enhancement strategy is mainly divided into two aspects, i.e. component enhancement and process optimization. The technologies for organic group enhancement, polymer crosslinking and fiber enhancement are relatively mature. The simple blending of silicon sources containing organic groups can effectively increase the macromolecular chain segments and improve the compressive strength and elasticity of the material. When polymer crosslinking is used, the mechanical properties of aerogels are improved by introducing organic groups on the hydroxyl groups of silica aerogels and coating organic layers on the outer layer of the slender silicon skeleton. The active groups of different polymers can give different structures and properties of silica aerogels. When the fiber is used as the reinforcing phase, a more stable three-dimensional network can be formed by physical entanglement to improve the flexibility and structural stability of the aerogel composite. In terms of process optimization, two new processes of bionic drying technology and 3D printing technology are mainly introduced. Through detailed analysis of the problems existing in the flexible enhancement research, it is proposed that the component enhancement should be carried out by properly selecting the silane precursor and compounding it with organic polymer or fiber to construct a flexible network skeleton to create the regulation of chemical structure and network skeleton. In terms of process optimization, bionic drying technology has greater comprehensive advantages than atmospheric pressure drying. 3D printing technology can prepare a variety of geometric shapes of materials, which has potential application value for thermal insulation materials and medical fields.

Conclusion and Prospect The preparation of flexible aerogel composites with light heat insulation and good mechanical properties is the future development direction. In terms of component enhancement, the preparation process of organic group enhancement method is relatively simple and easy to achieve results, but the space for improvement is still limited because of the singular inorganic skeleton structure. The introduction of different polymers in the precursor solution can give aerogels different properties, and the study of the crosslinking mechanism is conducive to optimizing the enhancement process. It is feasible to use fibers with different characteristics as reinforcing phases. Different preparation processes can obtain aerogel fiber composites with different molding effects, which solves the problem of direct application of silicon-based aerogels. In terms of process optimization, exploring new bionic drying technology provides a new idea for the optimization of aerogel preparation process. It is worth noting that the new 3D printing technology can meet the design requirements of special material components. Finally, the breakthrough of ambient pressure drying technology, the development of polymer crosslinking or nanofiber reinforced preparation of flexible composite aerogels with orderly and controllable structure are prospected.

Key words: flexible reinforced, silica aerogels, thermal insulation, polymer cross-linking, structure control

中图分类号: 

  • O648.18

图1

多孔SiO2气凝胶的微观结构"

图2

SiO2气凝胶的弯曲性能和压缩性能示意图"

图3

气凝胶常压干燥工艺与仿生干燥工艺的对比"

图4

具有高几何复杂度的3D打印气凝胶材料"

[1] PIERRE A C, PAJONK G M. Chemistry of aerogels and their applications[J]. Chemical Reviews, 2002, 102 (11): 4243-4265.
pmid: 12428989
[2] DU A, WANG H, ZHOU B, et al. Multifunctional silica nanotube aerogels inspired by polar bear hair for light management and thermal insulation[J]. Chemistry of Materials, 2018, 30 (19): 6849-6857.
doi: 10.1021/acs.chemmater.8b02926
[3] ZHAO X, WANG W, WANG Z, et al. Flexible PEDOT: PSS/polyimide aerogels with linearly responsive and stable properties for piezoresistive sensor applications[J]. Chemical Engineering Journal, 2020. DOI: 10.1016/j.cej.2020.125115.
doi: 10.1016/j.cej.2020.125115
[4] ABDULLAH H B, IRMAWATI R, ISMAIL I, et al. Direct synthesis of carbon nanotube aerogel using floating catalyst chemical vapor deposition: effect of gas flow rate[J]. Chemical Papers, 2020, 74 (10): 3359-3365.
doi: 10.1007/s11696-020-01166-6
[5] HUANG D M, GUO C N, ZHANG M Z, et al. Characteristics of nanoporous silica aerogel under high temperature from 950 ℃ to 1 200 ℃[J]. Materials & Design, 2017, 129: 82-90.
[6] 蒋璐璐, 邓梦, 王云仪, 等. 气凝胶材料在消防服中的应用研究进展[J]. 纺织学报, 2021, 42(9): 187-194.
JIANG Lulu, DEBG Meng, WANG Yunyi, et al. Research progress on application of aerogel materials in firefighting clothing[J]. Journal of Textile Research, 2021, 42(9): 187-194.
[7] GYORI E, VARGA A, FABIAN I, et al. Supercritical CO2 extraction and selective adsorption of aroma materials of selected spice plants in functionalized silica aerogels[J]. The Journal of Supercritical Fluids, 2019, 148: 16-23.
doi: 10.1016/j.supflu.2019.02.025
[8] LI M Z, JIA L C, ZHANG X P, et al. Robust carbon nanotube foam for efficient electromagnetic interference shielding and microwave absorption[J]. Journal of Colloid and Interface Science, 2018, 530: 113-119.
doi: 10.1016/j.jcis.2018.06.052
[9] 盛宇, 徐丽慧, 孟云, 等. 用SiO2/TiO2复合气凝胶制备超疏水光催化防紫外线织物[J]. 纺织学报, 2019, 40(7): 90-96.
SHENG Yu, XU Lihui, MENG Yun, et al. Preparation of superhydrophobic, photocatalytic and UV-blocking textiles based on SiO2/TiO2 composite aerogels[J]. Journal of Textile Research, 2019, 40(7): 90-96.
[10] WANG Q, YU H, ZHANG Z Y, et al. One-pot synthesis of polymer-reinforced silica aerogels from high internal phase emulsion templates[J]. Journal of Colloid and Interface Science, 2020, 573: 62-70.
doi: S0021-9797(20)30419-7 pmid: 32259693
[11] VENKATARAMAN M, MISHRA R, KOTRESH T M, et al. Aerogels for thermal insulation in high-performance textiles[J]. Textile Progress, 2016, 48 (2): 55-118.
doi: 10.1080/00405167.2016.1179477
[12] MALFAIT W J, ZHAO S Y, VEREL R, et al. Surface chemistry of hydrophobic silica aerogels[J]. Chemistry of Materials, 2015, 27 (19): 6737-6745.
doi: 10.1021/acs.chemmater.5b02801
[13] BAETENS R, JELLE B P, GUSTAVSEN A. Aerogel insulation for building applications: a state-of-the-art review[J]. Energy and Buildings, 2011, 43 (4): 761-769.
doi: 10.1016/j.enbuild.2010.12.012
[14] LI C D, CHEN Z F, DONG W F, et al. A review of silicon-based aerogel thermal insulation materials: performance optimization through composition and microstructure[J]. Journal of Non-Crystalline Solids 2021. DOI: 10.1016/j.jnoncrysol.2020.120517.
doi: 10.1016/j.jnoncrysol.2020.120517
[15] PADMANABHAN S K, Ul HAQ E, LICCIULLI A, et al. Synthesis of silica cryogel-glass fiber blanket by vacuum drying[J]. Ceramics International, 2016, 42(6): 7216-7222.
doi: 10.1016/j.ceramint.2016.01.113
[16] TORRES R B, VAREDA J P, LAMY-MENDES A, et al. Effect of different silylation agents on the properties of ambient pressure dried and supercritically dried vinyl-modified silica aerogels[J]. The Journal of Supercritical Fluids, 2019, 147: 81-89.
doi: 10.1016/j.supflu.2019.02.010
[17] WANG Y F, LI Z, HUBER L, et al. Reducing the thermal hazard of hydrophobic silica aerogels by using dimethyldichlorosilane as modifier[J]. Journal of Sol-Gel Science and Technology, 2020, 93 (1): 111-122.
doi: 10.1007/s10971-019-05170-5
[18] KARAMIKAMKAR S, NAGUIB H E, PARK C B. Advances in precursor system for silica-based aerogel production toward improved mechanical properties, customized morphology, and multifunctionality: a review[J]. Advances in Colloid and Interface Science, 2020. DOI: 10.1016/j.cis.2020.102101.
doi: 10.1016/j.cis.2020.102101
[19] WANK L K, FENG J Z, JIANG Y G, et al. Polyvinylmethyldimethoxysilane reinforced methyltrime-thoxysilane based silica aerogels for thermal insulation with super-high specific surface area[J]. Materials Letters, 2019. DOI: 10.1016/j.matlet.2019.126644.
doi: 10.1016/j.matlet.2019.126644
[20] RAO A V, BHAGAT S D, HIRASHIMA H, et al. Synthesis of flexible silica aerogels using methyltrimethoxysilane (MTMS) precursor[J]. Journal of Colloid and Interface Science, 2006, 300 (1): 279-285.
pmid: 16707131
[21] LIU C, WU S J, YANG Z F, et al. Mechanically robust and flame-retardant silicon aerogel elastomers for thermal insulation and efficient solar steam generation[J]. ACS Omega, 2020, 5 (15): 8638-8646.
doi: 10.1021/acsomega.0c00086 pmid: 32337427
[22] HAYASE G, KANAMORI K, HASEGAWA G, et al. A superamphiphobic macroporous silicone monolith with marshmallow-like flexibility[J]. Angewandte Chemie, 2013, 52 (41): 10788-10791.
[23] SHIMIZU T, KANAMORI K, NAKANISHI K. Silicone-based organic-inorganic hybrid aerogels and xerogels[J]. Chemistry: A European Journal, 2017, 23 (22): 5176-5187.
doi: 10.1002/chem.v23.22
[24] MALEKI H, DURAES L, PORTUGAL A, et al. Synthesis of lightweight polymer-reinforced silica aerogels with improved mechanical and thermal insulation properties for space applications[J]. Microporous and Mesoporous Materials, 2014, 197: 116-129.
doi: 10.1016/j.micromeso.2014.06.003
[25] CHOI H, PARALE V G, KIM T, et al. Structural and mechanical properties of hybrid silica aerogel formed using triethoxy (1-phenylethenyl) silane[J]. Microporous and Mesoporous Materials, 2020. DOI: 10.1016/j.micromeso.2020.110092.
doi: 10.1016/j.micromeso.2020.110092
[26] ZU G Q, KANAMORI K, MAENO A, et al. Superflexible multifunctional polyvinylpoly dimethylsiloxane-based aerogels as efficient absorbents, thermal superinsulators, and strain sensors[J]. Angewandte Chemie International Edition, 2018, 57(31): 9722-9727.
doi: 10.1002/anie.v57.31
[27] WU X D, MAN J W, LIU S J, et al. Isocyanate-crosslinked silica aerogel monolith with low thermal conductivity and much enhanced mechanical properties: fabrication and analysis of forming mechanisms[J]. Ceramics International, 2021, 47 (19): 26668-26677.
doi: 10.1016/j.ceramint.2021.06.074
[28] JAXEL J, MARKEVICIUS G, RIGACCI A, et al. Thermal superinsulating silica aerogels reinforced with short man-made cellulose fibers[J]. Composites Part A: Applied Science and Manufacturing, 2017, 103: 113-121.
doi: 10.1016/j.compositesa.2017.09.018
[29] KEHRLE J, PURKAIT T K, KAISER S, et al. Super-hydrophobic silicon nanocrystal-silica aerogel hybrid materials: synthesis, properties, and sensing appli-cation[J]. Langmuir, 2018, 34 (16): 4888-4896.
doi: 10.1021/acs.langmuir.7b03746
[30] AOKI Y, SHIMIZU T, KANAMORI K, et al. Low-density, transparent aerogels and xerogels based on hexylene-bridged polysilsesquioxane with bend-ability[J]. Journal of Sol-Gel Science and Technology, 2017, 81(1), 42-51.
doi: 10.1007/s10971-016-4077-1
[31] 李健, 张恩爽, 刘圆圆, 等. 超低密度气凝胶的制备及应用[J]. 化学进展, 2020, 32(6): 713-726.
doi: 10.7536/PC191016
LI Jian, ZHANG Enshuang, LIU Yuanyuan, et al. Preparation of the ultralow density aerogel and its application[J]. Progress in Chemistry, 2020, 32(6): 713-726.
doi: 10.7536/PC191016
[32] LI H M, LI J H, THOMAS A, et al. Ultra-high surface area nitrogen-doped carbon aerogels derived from a schiff-base porous organic polymer aerogel for CO2 storage and supercapacitors[J]. Advanced Functional Materials, 2019. DOI:10.1002/adfm.201904785.
doi: 10.1002/adfm.201904785
[33] YU Z L, YANG N, APOSTOLOPOULOU- KALKAVOURA V, et al. Fire-retardant and thermally insulating phenolic-silica aerogels[J]. Angewandte Chemie-International Edition 2018, 57 (17): 4538-4542.
doi: 10.1002/anie.v57.17
[34] WANG X, LU L L, YU Z L, et al. Scalable template synthesis of resorcinol-formaldehyde/graphene oxide composite aerogels with tunable densities and mechanical properties[J]. Angewandte Chemie International Edition, 2015, 54 (8): 2397-2401.
doi: 10.1002/anie.201410668
[35] ZHANG R B, AN Z M, ZHAO Y, et al. Nanofibers reinforced silica aerogel composites having flexibility and ultra-low thermal conductivity[J]. International Journal of Applied Ceramic Technology, 2020, 17 (3): 1531-1539.
doi: 10.1111/ijac.v17.3
[36] UI Haq E, ZAIDI S F A, ZUBAIR M, et al. Hydrophobic silica aerogel glass-fibre composite with higher strength and thermal insulation based on methyltrimethoxysilane (MTMS) precursor[J]. Energy and Buildings, 2017, 151: 494-500.
doi: 10.1016/j.enbuild.2017.07.003
[37] HE J, ZHAO H Y, LI X L, et al. Large-scale and ultra-low thermal conductivity of ZrO2 fibrofelt/ZrO2-SiO2 aerogels composites for thermal insulation[J]. Ceramics International, 2018, 44(8): 8742-8748.
doi: 10.1016/j.ceramint.2018.01.089
[38] 姚鸿俊, 王飞, 朱召贤, 等. 柔性有机硅气凝胶复合材料的制备及性能研究[J]. 宇航材料工艺, 2019, 49(6):26-32.
YAO Hongjun, WANG Fei, ZHU Zhaoxian, et al. Preparation and properties of flexible silicone aerogel composites[J]. Aerospace Materials & Technology, 2019, 49(6):26-32.
[39] LI Z, CHENG X D, HE S, et al. Aramid fibers reinforced silica aerogel composites with low thermal conductivity and improved mechanical performance[J]. Composites Part A: Applied Science and Manufacturing, 2016, 84: 316-325.
doi: 10.1016/j.compositesa.2016.02.014
[40] LI X H, YANG Z C, SHAO H L, et al. The influence of chopped PI fibers on thermal, mechanical and sound insulation properties of methylsilsesquioxane aerogels[J]. Journal of Sol-Gel Science and Technology, 2022, 101:519-528.
doi: 10.1007/s10971-021-05701-z
[41] FU J J, HE C X, HUANG J D, et al. Cellulose nanofibril reinforced silica aerogels: optimization of the preparation process evaluated by a response surface methodology[J]. RSC Advances, 2016, 6 (102): 100326-100333.
doi: 10.1039/C6RA20986F
[42] SI Y, WANG X Q, DOU L Y, et al. Ultralight and fire-resistant ceramic nanofibrous aerogels with temperature-invariant superelasticity[J]. Science Advances, 2018. DOI: 10.1126/sciadv.aas8925.
doi: 10.1126/sciadv.aas8925
[43] PATIL S P, SHENDYE P, MARKERT B, et al. Mechanical properties and behavior of glass fiber-reinforced silica aerogel nanocomposites: insights from all-atom simulations[J]. Scripta Materialia, 2020, 177:65-68.
doi: 10.1016/j.scriptamat.2019.10.010
[44] CHENG H M XUE, HONG C Q, et al. Preparation, mechanical, thermal and ablative properties of lightweight needled carbon fibre felt/phenolic resin aerogel composite with a bird's nest structure[J]. Composites Science and Technology, 2017, 140:63-72.
doi: 10.1016/j.compscitech.2016.12.031
[45] 乐弦, 陈俊勇, 李华鑫, 等. 气凝胶材料的结构强化研究进展[J]. 硅酸盐学报, 2021, 49(4):681-691.
YUE Xian, CHEN Junyong, LI Huaxin, et al. Research progress in structure strengthening of aerogels[J]. Journal of The Chinese Ceramic Society, 2021, 49(4):681-691.
[46] SMALLSHIRE D, SWASH A. Britain's dragonflies: a field guide to the damselflies and dragonflies of britain and ireland-fully revised and updated third edition[M]. 3rd ed. Princeton: Princeton University Press, 2014:194-196.
[47] HAN X, HASSAN K T, HARVEY A, et al. Bioinspired synthesis of monolithic and layered aerogels[J]. Advanced Materials, 2018. DOI:10.1002/adma.201706294.
doi: 10.1002/adma.201706294
[48] CUCE E, CUCE P M, WOOD C J, et al. Optimizing insulation thickness and analysing environmental impacts of aerogel-based thermal superinsulation in buildings[J]. Energy and Buildings, 2014, 77:28-39.
doi: 10.1016/j.enbuild.2014.03.034
[49] IGLESIAS-MEJUTO A, GARCIA-GONZALEZ C A. 3D-printed alginate-hydroxyapatite aerogel scaffolds for bone tissue engineering[J]. Materials Science & Engineering C:Materials for Biological Applications, 2021. DOI: 10.1016/j.msec.2021.112525.
doi: 10.1016/j.msec.2021.112525
[50] LIU D P, CHEN C J, ZHOU Y B, et al. 3D-printed, high-porosity, high-strength graphite aerogel[J]. Small Methods, 2021. DOI: 10.1002/smtd.202001188.
doi: 10.1002/smtd.202001188
[51] TANG X W, ZHOU H, CAI Z C, et al. Generalized 3D printing of graphene-based mixed-dimensional hybrid aerogels[J]. ACS Nano, 2018, 12 (4): 3502-3511.
doi: 10.1021/acsnano.8b00304 pmid: 29613763
[52] ZHANG Q Q, ZHANG F, MEDARAMETLA S P, et al. 3D printing of graphene aerogels[J]. Small, 2016, 12(13): 1702-1708.
doi: 10.1002/smll.201503524 pmid: 26861680
[53] LI V C F, DUNN C K, ZHANG Z, et al. Direct ink write 3D printed cellulose nanocrystal aerogel structures[J]. Scientific Reports, 2017. DOI: 10.1021/acssuschemeng.7b03439.
doi: 10.1021/acssuschemeng.7b03439
[54] MALEKI H, MONTES S, HAYATI-ROODBARI N, et al. Compressible, thermally insulating, and fire retardant aerogels through self-assembling silk fibroin biopolymers inside a silica structure: an approach towards 3D printing of aerogels[J]. ACS Applied Materials & Interfaces, 2018, 10 (26): 22718-22730.
[55] FARRELL E S, SCHILT Y, MOSHKOVITZ M Y, et al. 3D printing of ordered mesoporous silica complex structures[J]. American Chemical Society, 2020, 20, 6598-6605.
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