SiO<sub>2</sub>气凝胶力学性能增强研究进展

展望; 时钒; 李丽霞; 陈乐; 陈明毅; 孔庆红; 张庆武

doi:10.13801/j.cnki.fhclxb.20230420.001

SiO₂气凝胶力学性能增强研究进展

doi: 10.13801/j.cnki.fhclxb.20230420.001

展望^1,,
时钒¹,
李丽霞^1, ,,
陈乐²,
陈明毅¹,
孔庆红¹,
张庆武³

1.
江苏大学　环境与安全工程学院，镇江 212013
2.
南京大学　电子科学与工程学院，南京 210046
3.
南京工业大学　安全科学与工程学院，南京 211800

基金项目: 国家自然科学基金(52004131)；国家自然科学基金(52204213)；江苏大学应急管理学院大学生科研训练培育项目(JG-03-07)

详细信息

通讯作者:
李丽霞，博士，副教授，硕士生导师，研究方向为功能材料的合成　E-mail:qingpipa@ujs.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2023-02-24
- 修回日期: 2023-03-27
- 录用日期: 2023-04-08
- 网络出版日期: 2023-04-21
- 刊出日期: 2023-09-15

Research progress on mechanical properties enhancement of SiO₂ aerogels

1.
School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China
2.
School of Electronic Science and Engineering, Nanjing University, Nanjing 211816, China
3.
College of Safety Science and Engineering, Nanjing Tech University, Nanjing 211816, China

Funds: National Natural Science Foundation of China (52004131)；National Natural Science Foundation of China (52204213)；The Students Scientific Research Training Program of College of Emergency Management of Jiangsu University (JG-03-07)

摘要

摘要: 随着社会飞速发展，潜伏的火灾隐患对社会安全造成巨大的威胁，使用防火隔热材料可以有效地进行火灾防控。气凝胶具有密度低、导热系数低、孔隙率高等特点，且呈现出优异的防火隔热性能。SiO₂气凝胶是气凝胶材料的典型代表，目前在诸多行业被广泛应用。但是目前SiO₂气凝胶仍存在力学性能较差的瓶颈问题，极大地限制了工程应用，因此需要通过引入增强体使SiO₂气凝胶保持其本身优良特性的同时需增强其力学性能。本文对目前增强SiO₂材料的研究现状进行了简述，并着重针对在制备SiO₂气凝胶过程中通过优化工艺及添加纳米材料、纤维、成型体来提高力学性能的方法进行了讨论分析。最后提出了SiO₂气凝胶未来的研究方向及发展的建议。
- 气凝胶 /
- 防火隔热 /
- 强度 /
- 优化工艺 /
- 纳米材料 /
- 纤维 /
- SiO₂ /
- 力学性能
Abstract: With the rapid development of society, latent fire hazards have a great threat to social security. Fire prevention and control can be effectively carried out by using fire insulation materials. Aerogels have the characteristics of low density, low thermal conductivity, high porosity, and exhibit excellent fire insulation properties. SiO₂ aerogel is the typical representative of aerogel materials and widely used in many industries. However, SiO₂ aerogel still has the bottleneck problem of poor mechanical properties at present, resulting in greatly limits for the engineering application. Therefore, it is necessary to introduce reinforcements to make SiO₂ aerogel maintain its own excellent characteristics and enhance its mechanical properties. In this paper, the current research status of reinforced SiO₂ materials is briefly described, then the methods of improving mechanical properties by optimizing the process and adding nanomaterials, fibers, compacts in the preparation of silica aerogels are discussed and analyzed. Finally, this paper proposed the future research direction and development suggestions of SiO₂ aerogels .
- aerogel /
- fireproof and heat insulation /
- strength /
- process optimization /
- nanomaterial /
- fiber /
- SiO₂ /
- mechanical properties

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图 1 SiO₂气凝胶力学性能增强方法

Figure 1. Mechanical property enhancement methods of silica aerogel

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图 2 柔性SiO₂气凝胶压缩结果^[35]

Figure 2. Compression result of flexible SiO₂ aerogel^[35]

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图 3 双介孔SiO₂气凝胶反应机制图：(a) 水解反应；((b)~(d)) 缩合反应^[37]

Figure 3. Mechanism of the double mesoporous SiO₂ aerogelchemical reactions: (a) Hydrolysis reaction; ((b)-(d)) Condensation reaction^[37]

TEOS—Tetraethyl orthosilicate; MTES—Methyl triethoxysilane; MT-0.3—TEOS∶MTES=0.3∶0.7 (Molar ratio); M-0—TEOS∶MTES=0∶1 (Molar ratio); T-1—TEOS∶MTES=1∶0 (Molar ratio)

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图 4 不同老化条件下制备的SiO₂气凝胶^[44]

Figure 4. SiO₂ aerogels prepared under different aging conditions^[44]

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图 5 SiO₂气凝胶刚度及密度随时间变化规律^[45]

Figure 5. Variation of stiffness and density of SiO₂ aerogel with time^[45]

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图 6 气凝胶颗粒转化过程的强化模型及不同温度热处理后三聚氰胺(MS)/SiO₂气凝胶SEM图像^[52]

Figure 6. Strengthen model of aerogel particles transformation process and SEM images of melamine (MS)/SiO₂ aerogels prepared by heat treatment at different temperatures^[52]

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图 7 不同温度处理后气凝胶SEM图像^[53]

Figure 7. SEM images of aerogel processed at different temperatures^[53]

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图 8 不同碳纳米管含量碳纳米管(CNTs)/SiO₂气凝胶图像^[62]

Figure 8. Images of carbon nanotubes (CNTs)/silica aerogels with different CNTs content^[62]

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图 9 CNT_S/SiO₂气凝胶的制备流程及SEM图像^[63]

Figure 9. Preparation process and SEM images of CNTs/SiO₂ aerogel^[63]

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图 10 氧化石墨烯(GO)/SiO₂气凝胶制备流程图^[70]

Figure 10. Preparation process of graphene oxide (GO)/SiO₂ aerogels^[70]

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图 11 (a) SiO₂/GO复合气凝胶形成的示意图；(b) SiO₂/GO-5.0复合材料HRTEM图像^[71]

Figure 11. (a) Schematic illustration of the formation of SiO₂/GO composite aerogels; (b) HRTEM images of SiO₂/GO-5.0 composites^[71]

5.0 in SiO₂/GO-5.0—Amount of GO added is 5.0wt%

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图 12 添加不同纳米纤维素(CNFs)及表面处理气凝胶的SEM图像：(a) 未改性CNF1；(b) 未改性 CNF2；(c) 改性 CNF1；(d) 改性 CNF2^[78]

Figure 12. SEM of aerogels with different nano cellulose (CNFs) and surface treatment: (a) Unmodified CNF1; (b) Unmodified CNF2; (c) Modified CNF1; (d) Modified CNF2^[78]

CNF1—Fine S: 94%, Fine P: 4.6%; CNF2—Fine S: 48%, Fine P: 23.5%

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图 13 CNF/SiO₂气凝胶应力-应变曲线^[78]

Figure 13. Stress-strain curves of CNF/SiO₂ aerogels^[78]

SS—Silica sol; M—TMCS modification; NCA1—5 mL CNF1+ 25 mL distilled water

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图 14 800^oC时石英纤维(QF)/Al₂O₃-SiO₂复合材料的SEM图像^[83]

Figure 14. SEM images of quartz fiber (QF)/Al₂O₃-SiO₂ composite at 800^oC^[83]

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图 15 (a) QF/SiO₂气凝胶的SEM图像；(b) 纤维搭接处SEM图像^[84]

Figure 15. (a) SEM image of QF/SiO₂ aerogel; (b) SEM image of joining of fibers^[84]

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图 16 玻璃纤维(GF)/SiO₂气凝胶制备工艺^[87]

Figure 16. Preparation technology of glass fiber (GF)/SiO₂ aerogel^[87]

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图 17 SiO₂气凝胶与气相SiO₂比例对SiO₂复合材料导热系数和弯曲模量的影响^[88]

Figure 17. Influence of the ratio of SiO₂ aerogel to the fumed SiO₂ on the thermal conductivity and flexural modulus of the SiO₂ composites^[88]

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图 18 纤维的分层结构分布^[94]

Figure 18. Layered structure of the fiber distribution^[94]

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图 19 硅酸铝纤维毡(ASF)/莫来石晶须(MW)/SiO₂气凝胶制备流程图^[96]

Figure 19. Preparation process of alumina silicate fiber felt (ASF)/mullite whisker (MW)/SiO₂aerogels^[96]

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图 20 (a) 碳纤维毡增强SiO₂气凝胶SEM图像；(b) 硅酸铝纤维毡增强 SiO₂气凝胶SEM图^[97]

Figure 20. (a) SEM images of carbon fiber felt reinforced SiO₂ aerogels; (b) SEM images of aluminum silicate fiber felt reinforced SiO₂ aerogel ^[97]

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图 21 不同温度下QF/SiO₂气凝胶的拉伸强度和断裂伸长率^[98]

Figure 21. Tensile strength and elongation at break of QF/silica aerogels at different temperatures^[98]

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图 22 GF/SiO₂气凝胶压缩实验：(a) 压缩前；(b) 压缩达到60%应变；(c) 压缩后完全恢复^[99]

Figure 22. Compression test of GF/SiO₂ aerogels: (a) Before compression; (b) Compression up to 60% strain; (c) Recovered fully after compression^[99]

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图 23 网状聚氨酯泡沫及不同泡孔尺寸结构显微照片^[100]

Figure 23. Microstructure of reticulated polyurethane foam and different cell sizes^[100]

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图 24 泡沫陶瓷@二氧化硅气凝胶(FG@SA)和泡沫玻璃@二氧化硅气凝胶(FG@SA)结构示意图^[101]

Figure 24. Demonstration diagram of ceramic foam@SiO₂ aerogels(FG@SA) and foam glass@SiO₂ aerogels(FG@SA) structure^[101]

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表 1 SiO₂气凝胶样品的初始组成^[35]

Table 1. Starting compositions of SiO₂ aerogel samples^[35]

Sample	V(EtOH)∶V(H₂O)	V(TMCS)∶M(CTAB)
S-14	1∶14	0∶0.1
S-13	2∶13	0∶0.1
S-12	3∶12	0∶0.1
S-11	4∶11	0∶0.1
S-10	5∶10	0∶0.1
S-14 m	1∶14	4∶0.1
S-11 m	1/11	4∶0.1
Notes: EtOH—Absolute ethyl alcohol; TMCS—Trimethylchlorosilane; CTAB—Cetyltrimethyl ammonium bromide; V—Volume, mL; M—Mass, g.

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表 2 不同途径增强后气凝胶的热-力性能

Table 2. Thermo-mechanical properties of aerogel after enhancement by different approaches

Enhancement methods	Mechanical property	Thermal conductivity/(W·(m·K)⁻¹)
Silicon source^[36]	Young’s modulus: 56 kPa	0.0343
Aging^[44-45]	Young’s modulus: 0.117 MPa	0.027
Heat treatment^[52]	Maximum stress: 0.764 MPa (40% strain)	0.0278
CNTs^[63]	Young’s modulus: 201.5 kPa	0.0312
GO^[72]	Compressive strength: 0.65 MPa	0.018
CNF^[78]	Compressive strength: 95.4 kPa Young’s modulus: 122.2 kPa	0.023
Quartz fiber^[84]	Bending strength: 2.34 MPa	0.0335
Glass fiber^[85]	Young’s modulus: 1393 kPa	0.0213
Ceramic fiber^[93]	Compressive strength: 0.1082 MPa(10% strain)	0.101
Aramid fiber^[94]	Young’s modulus: 0.14 MPa	0.0227
Fiber felt^[96]	Compressive strength: 2.33 MPa (25% strain)	0.0373
Blown foam^[100]	Young’s modulus: 307 kPa	0.0123

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