Preparation and properties of anisotropic cellulose nanofiber/aramidnanofiber composite foam
-
摘要: 纤维素纳米纤维(CNF)泡沫材料因为其轻质、可生物降解、可再生性以及优良的隔热性能等特点，在保温隔热领域备受关注。但是CNF泡沫存在力学性能差、热稳定性差、易燃等缺点，在一定程度限制了其实际应用。本文通过将CNF与芳纶纳米纤维(ANF)进行复合，通过冰模板法和冷冻干燥技术制备了具有各向异性结构的CNF/ANF复合泡沫。探究了ANF添加量和各向异性结构的引入对复合泡沫微观结构、力学性能、热稳定性和隔热性能的影响。结果表明，当CNF和ANF的质量比为2∶1时，CNF/ANF复合泡沫具有超低的密度(12.25 mg/cm3)，良好的力学强度(纵向压缩强度为74.56 kPa)和优异的隔热性能(25.2 mW/mk)，此外，该复合泡沫还具有良好的热稳定性和自熄灭性能，这些特性赋予了其在保温隔热等领域更加广阔的应用前景。Abstract: Cellulose nanofibers (CNF) foam has gained attention in the field of thermal insulation due to its lightweight, biodegradable, renewable nature, and excellent insulation properties.. However, CNF foam suffers from drawbacks such as poor mechanical properties, flammability, and limited thermal stability, which restrict their practical applications. This study prepares anisotropic CNF/ANF composite foam by introducing aramid nanofibers (ANF) into nanocellulose fibers, using ice templating method combined with freeze-drying technique. The effects of ANF content and the introduction of anisotropic structure on the microstructure, mechanical properties, thermal stability, and thermal insulation performance of the composite foam were investigated. The results showed that,when the mass ratio of CNF to ANF is 2∶1, the CNF/ANF composite foam exhibits an ultra-low density (12.25 mg/cm3), good mechanical strength (axial compressive strength of 74.56 kPa), and excellent thermal insulation performance (25.2 mW/mk). Additionally, this composite foam also possesses good thermal stability and flame retardant properties, which endow it with broad prospects for applications in areas such as insulation and self-extinguishing property.
-
图 1 各向异性纤维素纳米纤维(CNF)/芳纶纳米纤维(ANF)复合泡沫的制备流程图
Figure 1. Schematic of the preparation of anisotropic Cellulose nanofibers (CNF)/ aramid nanofibers (ANF) composite foam
图 3 CNF1ANF0、CNF1ANF1、CNF0ANF1复合泡沫的XPS全谱图(a); C1 s 精细谱：CNF1ANF0(b);CNF1ANF1(c); CNF0ANF1(d)
Figure 3. XPS full spectrum of CNF1ANF0, CNF1ANF1, and CNF0ANF1 composite foam (a); C1 s high-resolution spectra: CNF1ANF0 (b),CNF1ANF1 (c), CNF0ANF1 (d)
图 4 CNF/ANF复合泡沫纵切面和横切面上的SEM照片：(a1, a2) CNF1ANF0, (b1,b2) CNF3ANF1, (c1,c2) CNF2ANF1, (d1,d2) CNF1ANF1, (e1,e2) CNF1ANF2, (f1,f2) CNF1ANF3, (g1,g2) CNF0ANF1
Figure 4. SEM images of CNF/ANF composite foam at axial and radial section: (a1, a2) CNF1ANF0, (b1,b2) CNF3ANF1, (c1,c2) CNF2ANF1, (d1,d2) CNF1ANF1, (e1,e2) CNF1ANF2, (f1,f2) CNF1ANF3 , (g1,g2) CNF0ANF1
图 5 为CNF/ANF复合泡沫的纵向压缩应力-应变曲线(a)，横向压缩应力-应变曲线(b)， 80%压缩应变对应的应力图(c)，纵向/横向弹性模量图(d)
Figure 5. (a) Axial compression stress-strain curve; (b) Radial compression stress-strain curve; (c) Compressive stress at 80% strain; (d) Axial/radial elastic modulus graph of CNF/ANF composite foam
图 6 CNF/ANF复合泡沫的TG(a)和DTG曲线(b)
Figure 6. TG (a) and DTG (b) curves of CNF/ANF composite foam
图 8 CNF2ANF1在纵向(上)和横向(下)方向在180℃加热10、20、30、60 min的红外热成像图
Figure 8. The infrared thermal images of CNF2ANF1 in the axial (top) and radial (bottom) directions after heating at 180℃ for 10, 20, 30, and 60 minutes
表 1 CNF1ANF0、CNF1ANF1、CNF0ANF1复合泡沫的元素含量分析
Table 1. Element content analysis of CNF1ANF0, CNF1ANF1, and CNF0ANF1 composite foam
Sample C/% N/% O/% CNF1ANF0 56.21 0.61 43.18 CNF1ANF1 53.72 2.79 43.49 CNF0ANF1 72.36 13.68 13.96 
下载: 导出CSV
表 2 不同配比的CNF/ANF复合泡沫的密度、孔隙率以及收缩率
Table 2. Density, porosity and shrinkage of CNF/ANF composite foam with different ratios
Sample Density/(mg·cm−3) Porosity/% Shrinkage ratio/% CNF1ANF0 13.67±0.59 99.07±0.04 18.30±0.05 CNF3ANF1 12.57±0.88 99.15±0.06 17.02±0.14 CNF2ANF1 12.25±1.02 99.16±0.07 16.58±0.11 CNF1ANF1 12.63±1.41 99.13±0.1 16.40±0.07 CNF1ANF2 12.92±0.65 99.10±0.05 16.56±0.08 CNF1ANF3 11.11±0.86 99.26±0.09 16.25±0.012 CNF0ANF1 11.49±0.96 98.97±0.07 15.50±0.07
下载: 导出CSV
-
[1] YU Z, YANG N, APOSTOLOPOULOU V, et al. Fire-Retardant and Thermally Insulating P-henolic-Silica Aerogels[J]. Angewandte Chemie, 2018, 130(17): 4628-4632. doi: 10.1002/ange.201711717 [2] MOON R J, MARTIN A, NAIRN J, et al. Cellulose n-anomaterials review: structure, properties and n-anocomposites[J]. Chemical Society Reviews, 2011, 40(7): 3941. doi: 10.1039/c0cs00108b [3] 陈一鸣. 各向异性纳米纤维素气凝胶的结构调控及其性能影响机制研究[D]. 南京林业大学, 2021.CHEN Y M. Structure Control and Mechanism Investigation of Anisotropic Nanocellulose Aer-ogels and Their Performance Effects [D]. Nanji-ng Forestry University, 2021. (in chinese [4] ZHENG R, HU J, LIN Z, et al. Anisotropic Polyim-ide/Cellulose Nanofibril Composite Aerogels for Thermal Insulation and Flame Retardancy[J]. ACS Applied Polymer Materials, 2023, 5(6): 41804189. [5] 桓珊, 赵国栋, 李晓捷, 等. 芳纶复合纳米纤维气凝胶的制备及其性能研究[J]. 合成纤维, 2021, 50(6): 30-35.HUAN S, ZHAO G D, LI X J, et al. Preparation and Performance Study of Aromatic Polyamide Composite Nanofiber Aerogels[J]. Synthetic Fi-ber. (in chinese [6] XIE C, LIU S, ZHANG Q, et al. Macroscopic-Scale Preparation of Aramid Nanofiber Aerogel by Modified Freezing-Drying Method[J]. ACS Na-no, 2021, 15(6): 10000-10009. doi: 10.1021/acsnano.1c01551 [7] 黄连青. 芳纶纳米纤维高效制备及其有序结构凝胶构筑机制的研究[D]. 陕西科技大学, 2022.HUANG L Q. Efficient Preparation of Aromatic Polyamide Nanofibers and Study on the Mecha-nism of Ordered Structure Gel Construction [D]. Shaanxi University of Science and Technology. (in chinese [8] 刘增伟. 芳纶气凝胶纤维的制备表征及应用[D]. 中国科学技术大学, 2022.LIU Z W. Preparation, Characterization, and Ap-plication of Aromatic Polyamide Aerogel Fibers [D]. University of Science and Technology of C-hina. (in chinese [9] ZHENG J, HANG T, Li Z, et al. High-performance and multifunctional conductive aerogel films for outstanding electromagnetic interference shield-i-ng, Joule heating and energy harvesting[J]. Ch-e-mical Engineering Journal, 2023, 471: 144548. [10] LIU Q, SGENG M, DUAN C, et al. 3D Hierarchical Porous Carbon Aerogel Electrocatalysts Based on Cellulose/Aramid Nanofibers and Applicatio-n in High-Performance Zn–Air Batteries[J]. AC-S Applied Energy Materials, 2022, 5(12): 15146-15154. doi: 10.1021/acsaem.2c02801 [11] 胡锦澜, 李嘉杰, 张彦飞, 等. 环氧树脂/多巴胺增强芳纶纤维界面性能[J]. 工程塑料应用, 2023, 51(4): 36-41.HU J L, LI J J, ZHANG Y F, et al. Interface Per-formance of Epoxy Resin/Dopamine Reinforced Aromatic Aramid Fiber[J]. Engineering Plast-ics Application, 2023, 51(4): 36-41. (in chinese [12] YANG B, WANG L, ZHANG M, et al. Fabrication, A-pplications, and Prospects of Aramid Nanofiber[J]. Advanced Functional Materials, 2020, 30(22): 2000186. doi: 10.1002/adfm.202000186 [13] YANG B, WANG L, ZHANG M, et al. Timesaving, High-Efficiency Approaches To Fabricate Aram-id Nanofibers[J]. ACS Nano, 2019, 13(7): 7886-7897. doi: 10.1021/acsnano.9b02258 [14] MAITI S, JAYARAMUDU J, DAS K, et al. Preparation and characterization of nano-cellulose with new shape from different precursor[J]. Carbohydrate Polymers, 2013, 98(1): 562-567. doi: 10.1016/j.carbpol.2013.06.029 [15] WANG S. Thermal insulating, light-weight and c-onductive cellulose/aramid nanofibers composit-e aerogel for pressure sensing[J]. Carbohydrate Polymers, 2021. [16] 张艳, 马忠雷, 李桢, 等. 轻质高强MXene/细菌纤维素复合气凝胶的制备及其电磁屏蔽性能[J]. 复合材料学报, 2023, 40(11): 6409-6417. doi: 10.13801/j.cnki.fhclxb.20230109.003ZHANG Y, MA Z L, LI Z, et al. Preparation and EMI shielding properties of lightweight and mechanically strong MXene/bacterial cellulose composite aerogels[J]. Acta Materiae Compo-sitae Sinica, 2023, 40(11): 6409-6417(in Chinese). doi: 10.13801/j.cnki.fhclxb.20230109.003 [17] YANG M, ZHAO N, CUI Y, et al. Biomimetic Arch-itectured Graphene Aerogel with Exceptional St-rength and Resilience[J]. ACS Nano, 2017, 11(7): 6817-6824. doi: 10.1021/acsnano.7b01815 [18] YANG X, CRANSTON E D. Chemically Cross-Link-ed Cellulose Nanocrystal Aerogels with Shape Recovery and Superabsorbent Properties[J]. Ch-emistry of Materials, 2014, 26(20): 6016-6025. doi: 10.1021/cm502873c [19] ZHANG J, CHANG Y, TEBYETEKERWA M, et al. “Stiff–Soft” Binary Synergistic Aerogels with Superf-lexibility and High Thermal Insulation Perform-ance[J]. Advanced Functional Materials, 2019, 29(15): 1806407. doi: 10.1002/adfm.201806407 [20] APOSTOLOPOULOU V, MUNIER P, BERGSTROM L. Thermally Insulating Nanocellulose-Bas-ed Materials[J]. Advanced Materials, 2021, 33(28): 2001839. doi: 10.1002/adma.202001839 [21] WICKLEIN B, KOCJAN A, SALAZAR G, et al. Thermally insulating and fire-retardant lightwei-ght anisotropic foams based on nanocellulose a-nd graphene oxide[J]. Nature Nanotechnology, 2015, 10(3): 277-283. doi: 10.1038/nnano.2014.248 [22] JIANG S, ZHANG M, JIANG W, et al. Multiscale na-nocelluloses hybrid aerogels for thermal insulat-ion: The study on mechanical and thermal prop-erties[J]. Carbohydrate Polymers, 2020, 247: 116701. doi: 10.1016/j.carbpol.2020.116701 [23] Zuo X, CHANG K, ZHAO J, et al. Bubble-template-assisted synthesis of hollow fullerene-like MoS2nanocages as a lithium ion battery anode materi-al[J]. Journal of Materials Chemistry A, 2016, 4(1): 51-58. doi: 10.1039/C5TA06869J [24] SI Y, YU J, TANG X, et al. Ultralight nanofibre-as-sembled cellular aerogels with superelasticity a-nd multifunctionality[J]. Nature Communicatio-ns, 2014, 5(1): 5802. doi: 10.1038/ncomms6802 [25] JIANG S, ZHANG M, LI M, et al. Cellulose nanofiber (CNF) based aerogels prepared by a facile process and the investigation of thermal insulati-on performance[J]. Cellulose, 2020, 27(11): 6217-6233. doi: 10.1007/s10570-020-03224-4 [26] JAVADI A, ZHENG Q, PAYEN F, et al. Polyvinyl Al-cohol-Cellulose Nanofibrils-Graphene Oxide H-ybrid Organic Aerogels[J]. ACS Applied Materi-als & Interfaces, 2013, 5(13): 5969-5975. [27] DRUEL L, BARDL R, VORWERG W, et al. Starch Aero-gels: A Member of the Family of Thermal Super insulating Materials[J]. Biomacromolecules, 2017, 18(12): 4232-4239. doi: 10.1021/acs.biomac.7b01272 [28] YANG M, CAO K, SUI L, et al. Dispersions of Ara-mid Nanofibers: A New Nanoscale Building Block[J]. ACS Nano, 2011, 5(9): 6945-6954. doi: 10.1021/nn2014003 -
下载:
点击查看大图
计量
- 文章访问数: 221
- HTML全文浏览量: 185
- PDF下载量: 8
- 被引次数: 0
