高温隔热用微纳陶瓷纤维研究进展

doi:10.15541/jim20200220

无机材料学报 ›› 2021, Vol. 36 ›› Issue (3): 245-256.DOI: 10.15541/jim20200220 CSTR: 32189.14.10.15541/jim20200220

高温隔热用微纳陶瓷纤维研究进展

张晓山¹(), 王兵¹, 吴楠², 韩成¹, 吴纯治¹, 王应德¹()

1. 国防科技大学空天科学学院新型陶瓷纤维及其复合材料重点实验室, 长沙 410073
2. 国防科技大学空天科学学院材料科学与工程系, 长沙 410073

收稿日期:2020-04-26 修回日期:2020-06-09 出版日期:2021-03-20 网络出版日期:2020-09-09
通讯作者: 王应德, 教授. E-mail: wangyingde@nudt.edu.cn
作者简介:张晓山(1991-), 男, 博士研究生. E-mail: zhangxiaoshan15@nudt.edu.cn
基金资助:
国防基础科研计划(XXXX2016550C001);国防基础科研计划(XXXX2017550C001)

Micro-nano Ceramic Fibers for High Temperature Thermal Insulation

ZHANG Xiaoshan¹(), WANG Bing¹, WU Nan², HAN Cheng¹, WU Chunzhi¹, WANG Yingde¹()

1. Science and Technology on Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China
2. Department of Material Science and Engineering, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Received:2020-04-26 Revised:2020-06-09 Published:2021-03-20 Online:2020-09-09
Contact: WANG Yingde, professor. E-mail: wangyingde@nudt.edu.cn
About author:ZHANG Xiaoshan(1991-), male, PhD candidate. E-mail: zhangxiaoshan15@nudt.edu.cn
Supported by:
National Defense Basic Research Program(XXXX2016550C001);National Defense Basic Research Program(XXXX2017550C001)

摘要/Abstract

摘要：

陶瓷纤维具有密度低、强度高、耐高温、抗氧化和耐机械震动性能好等优点, 是空天飞行器、核能发电和化工冶金等热防护领域所需的关键高温隔热材料。传统陶瓷纤维直径粗(?>5 μm)、脆性大、热导率高, 在实际隔热领域应用中受到了极大限制。减小纤维直径, 制备微纳陶瓷纤维, 不仅有利于提高纤维力学性能, 还有望改善其高温隔热性能, 近年来引起了研究者的广泛关注。从微纳陶瓷纤维中影响热传输(气体热传导、固体热传导和辐射传热)的本征因素出发, 有针对地进行组成和结构优化, 进而改善其高温隔热性能, 是当前微纳陶瓷隔热纤维研究的重点方向。本文结合国内外研究现状, 在介绍微纳陶瓷纤维隔热机理的基础上, 按照纤维的组成和结构特点将目前微纳陶瓷隔热纤维分为三类, 即微纳陶瓷纤维气凝胶、中空/多孔微纳陶瓷纤维和复合微纳陶瓷纤维。对这三类不同特点的微纳陶瓷隔热纤维最新研究进展进行综述, 并展望了微纳陶瓷隔热纤维的未来发展方向。

关键词: 微纳陶瓷纤维, 高温隔热, 结构优化, 纤维气凝胶, 中空纤维, 复合纤维, 综述

Abstract:

Ceramic fiber has the advantages of low density, high strength, high temperature resistance and good mechanical vibration resistance. It is the critical high temperature thermal insulation materials especially in thermal protection fields such as aerospace vehicles, nuclear power plants and chemo-metallurgical industry, etc. The traditional ceramic fiber with large diameter (> 5 μm), high brittleness and high thermal conductivity has been greatly restricted in high temperature thermal insulation fields. In recent years, more and more attention has been paid to the preparation of micro-nano ceramic fibers by decreasing the diameter of fiber, which is not only beneficial to improve the mechanical properties of the fibers, but also to enhance their high temperature thermal insulation properties. Further, by finely regulating the composition and structure of the micro-nano ceramic fibers that intrinsically affecting the heat transfer (heat conduction of gas, heat conduction of solid and radiative heat transfer) mechanism in micro-nano ceramic fibers, the high temperature thermal insulation performance can be effectively improved, which is the current focus of the micro-nano ceramic fibers in high temperature thermal insulation fields. The thermal insulation mechanism of the micro-nano ceramic fibers was firstly introduced. Then, based on the research at home and abroad, this review divides the current micro-nano ceramic fibers into three categories according to the difference of their composition and structure, namely fibers aerogels, hollow/porous fibers and composite fibers. The latest research progress on composition and structure optimization of micro-nano ceramic fibers for high temperature thermal insulation is reviewed, and the future development tendency is prospected.

Key words: micro-nano ceramic fiber, high temperature thermal insulation, structural optimization, fiber aerogel, hollow fiber, composite fiber, review

中图分类号:

TQ343

张晓山, 王兵, 吴楠, 韩成, 吴纯治, 王应德. 高温隔热用微纳陶瓷纤维研究进展[J]. 无机材料学报, 2021, 36(3): 245-256.

ZHANG Xiaoshan, WANG Bing, WU Nan, HAN Cheng, WU Chunzhi, WANG Yingde. Micro-nano Ceramic Fibers for High Temperature Thermal Insulation[J]. Journal of Inorganic Materials, 2021, 36(3): 245-256.

图/表 11

图1 微纳陶瓷隔热纤维发展趋势示意图

Fig. 1 Schematic of development trend of the micro-nano ceramic fiber

图2 微纳陶瓷纤维热传导示意图(a), 不同温度下直径对碳纳米纤维热导率的影响(b)和不同温度条件下不同直径纤维红外透过率(c)[13,21]

Fig. 2 Schematic of micro-nano fiber heat conduction (a), effect of fiber diameter on thermal conductivity of carbon nanofiber at different testing temperatures (b), and transmittance values for fibers with different fiber diameters at different operating temperatures (c)[13,21]

图3 SiO2和SiC纳米纤维气凝胶[7-8,37] (a)SEM照片; (b)隔热性能测试红外成像照片; (c)压缩应力应变图; SiO2纳米纤维气凝胶的(d)SEM照片, (e)高温条件下压缩性能测试图和(f)热导率对比图; (g)SiC纳米纤维气凝胶的SEM照片, (h)隔热性能测试光学照片和(i)压缩应力应变曲线

Fig. 3 SiO2 and SiC nanofiber aerogel[7-8,37] (a,d) SEM images of SiO2 nanofiber aerogel; (b) Infrared thermal image; (c) Compression stress-strain; (e) Compression test under high temperature; (f) Thermal conductivity comparison; (g) SEM image of SiC nanofiber aerogel; (h) Optical photo of thermal insulation performance of SiC nanofiber aerogel; (i) Compression stress-strain of SiC nanofiber aerogel

图4 中空隔热纤维热传导示意图

Fig. 4 Schematic diagram of heat conduction of hollow fiber

图5 中空微纳陶瓷纤维[44,48] (a)中空ZrO2纤维表面和截面SEM照片; (b)中空ZrO2纤维与传统实芯ZrO2纤维热导率对比; (c)中空Al2O3纤维表面和截面SEM照片; (d)中空Al2O3纤维气凝胶与其他材料热导率对比

Fig. 5 Hollow micro-nano ceramic fiber[44,48] (a) Surface and cross section SEM images of hollow ZrO2 fiber; (b) Comparison of thermal conductivity between hollow ZrO2 fiber and traditional ZrO2 fiber; (c) Surface and cross section SEM images of hollow Al2O3 fiber; (d) Thermal conductivity comparison among hollow Al2O3 fiber aerogel and other materials

图6 中空碳纳米纤维气凝胶[49] (a)制备流程示意图; (b)TEM照片; (c)中空碳纳米纤维气凝胶经10000次压缩应力应变曲线及压缩测试图; (d)中空碳纳米纤维气凝胶与其他中空材料热导率比较

Fig. 6 Hollow carbon micro-nano fiber aerogel[49] (a) Schematic illustration of the fabrication processes; (b) TEM image; (c) Stress-strain curves for 10000 cycles; (d) Thermal conductivity comparison among different hollow-structured thermally insulating materials

图7 中空和多空微纳纤维[51-52,54] (a)氮掺杂中空SiC纤维SEM照片; (b)中空SiC纤维SEM照片; (c)多孔SiO2-TiO2纤维SEM照片; (d)氮掺杂中空SiC纤维热导率和热扩散系数; (e)中空和实芯SiC纤维热导率; (f)多孔SiO2-ZrO2纤维SEM照片

Fig. 7 Hollow and porous micro-nano fiber[51-52,54] (a) SEM image of N-doped hollow SiC fiber; (b) SEM image of hollow SiC fiber; (c)SEM image of porous SiO2-TiO2 fiber; (d) Thermal conductivities and thermal diffusivities of N-doped hollow SiC fiber; (e) Thermal conductivities of solid SiC fiber and hollow SiC fiber; (f) SEM image of SiO2-ZrO2 fiber

图8 红外辐射线在纤维中传输示意图

Fig. 8 Schematic of infrared radiation transmission in the fiber

表1 高反射率涂层纤维制备方法及涂层种类

Table 1 Preparation method and coating types of high-reflectivity coated fiber

Fiber	Method	Infrared reflectance layer	Coating thickness/μm	Ref.
Al₂O₃	Dip-coating	TiO₂, TiO₂/SiO₂/TiO₂, TiO₂-Pt	-	[64]
SiO₂	Dip-coating	ITO, ITO/Ag/ITO	~0.2	[60,65]
ZrO₂	Hydrothermal	CeO₂	52-214	[66]
Mullite	Hydrothermal	TiO₂	-	[67]
ZrO₂	Hydrothermal	TiO₂	89-236	[68]
Mullite	Dip-coating	SiC	~0.8	[69]

图9 高反射率涂层纤维[66-67,69] (a)CeO2/ZrO2纤维SEM照片; (b)TiO2/莫来石纤维SEM照片; (c)SiC/莫来石纤维表面SEM照片; (d)ZrO2纤维和CeO2/ZrO2纤维的比消光系数对比; (e)莫来石纤维和TiO2/莫来石纤维比消光系数对比; (f)莫来石纤维和SiC/莫来石纤维增强气凝胶复合材料热导率对比

Fig. 9 High-reflectivity coated fiber[66-67,69] (a) SEM image of ZrO2 fiber with CeO2 coating; (b) SEM image of mullite fiber with TiO2 coating; (c) SEM image of mullite fiber with SiC coating; (d) Specific extinction coefficients comparison of ZrO2 fiber and CeO2/ZrO2 fiber; (e) Specific extinction coefficients comparison of mullite fiber and TiO2/mullite fiber; (f) Thermal conductivity comparison of mullite fiber and SiC/mullite fiber reinforced aerogel composite

图10 复相微纳陶瓷纤维[14,70] (a)ZrO2/SiC纤维制备示意图; (b) ZrO2/SiC纤维TEM照片; (c) SiZrOC纤维SEM照片; (d) SiZrOC纤维热导率对比; (e) SiZrOC纤维隔热机理示意图

Fig. 10 Composite micro-nano ceramic fiber[14,70] (a) Schematic illustration of the preparation of ZrO2/SiC fiber; (b) TEM images of ZrO2/SiC fiber; (c) SEM images of SiZrOC fiber; (d) Thermal conductivity comparison of SiZrOC fiber with other ceramic fibers; (e) Schematic illustration of thermal insulation mechanisms of SiZrOC fibers

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高温隔热用微纳陶瓷纤维研究进展

Micro-nano Ceramic Fibers for High Temperature Thermal Insulation

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