碳纳米管对酚醛树脂基复合材料性能的影响

doi:10.12382/bgxb.2022.1042

摘要/Abstract

摘要：

为制备具有隔热、耐烧蚀、电磁屏蔽等多功能集成的结构复合材料,满足武器装备对多功能复合材料的迫切需求,采用超声波分散的工艺将碳纳米管(Carbon Nanotubes,CNTs)在树脂基体中进行分散,并制备CNTs改性国产碳布/酚醛复合材料。经对CNTs改性国产碳布/酚醛复合材料的层间性能检测,当CNTs含量达到1.5%时,其层间剪切强度提高57.4%。对CNTs改性定向国产碳纤维/酚醛树脂复合材料的弯曲性能、层间性能和抗冲击性能都进行检测。检测结果表明,经CNTs改性后,定向国产碳纤维/酚醛复合材料的力学性能和模量均得到了大幅提高。对CNTs改性短切高强玻璃纤维/酚醛树脂基复合材料的导电性能和导热性能进行了研究。研究结果表明:随着CNTs含量的提高,短切高强玻璃纤维/酚醛树脂基复合材料的电阻率呈数量级速度降低,当CNTs含量达到14%时,复合材料的电阻率由10¹⁰Ω·m降低到了10^-2Ω·m,复合材料由绝缘体转变为导体;当CNTs含量小于6%时,复合材料的导热系数虽有提高,但与复合材料电性能相比提高幅度不大。

关键词: 碳纳米管, 碳布/酚醛复合材料, 碳纤维/酚醛复合材料, 导电, 隔热

Abstract:

A multifunctional integrated structural composite material with heat insulation, erosion resistance, electromagnetic shielding, etc., is prepared to meet the urgent demand for multifunctional composite materials in weapons and equipment. In this paper, the carbon nanotubes are dispersed in the resin matrix by ultrasonic dispersion process, and the domestic carbon cloth/phenolic composites modified by carbon nanotubes are prepared. The interlaminar shear strength of domestic carbon cloth/phenolic composites modified by carbon nanotubes is increased by 57.4% when the content of carbon nanotubes reaches 1.5%. The bending properties, interlaminar properties and impact resistance of the oriented domestic carbon fiber/phenolic resin composites modified by carbon nanotubes were tested. The test results show that the mechanical properties and modulus of the oriented domestic carbon fiber/phenolic resin composites are significantly improved after the modification of carbon nanotubes. The electrical conductivity and thermal conductivity of carbon nanotube-modified chopped high-strength glass fiber/phenolic resin matrix composites are also studied. The results show that the resistivity of chopped high-strength glass fiber/phenolic resin matrix composites is decreaseed by an order of magnitude with the increase of carbon nanotube content. When the content of carbon nanotubes reaches 14%, the resistivity of the composites decreases from 10¹⁰Ω·m to 10^-2Ω·m, and The composites change from insulator to conductor. When the content of carbon nanotubes is less than 6%, the thermal conductivity of the composites is improved, but it is improved modestly compared with the electrical properties of the composites.

Key words: carbon nanotubes, carbon cloth/phenolic composite, carbon fiber/phenolic composite, electric conduction, heat insulation

中图分类号:

TB332

孔国强, 安振河, 赵寰, 于秋兵, 邵蒙, 李莹, 魏化震, 王康, 刘文博. 碳纳米管对酚醛树脂基复合材料性能的影响[J]. 兵工学报, 2024, 45(5): 1547-1554.

KONG Guoqiang, AN Zhenhe, ZHAO Huan, YU Qiubing, SHAO Meng, LI Ying, WEI Huazhen, WANG Kang, LIU Wenbo. Effect of Carbon Nanotubes on Properties of Phenolic Resin Matrix Composites[J]. Acta Armamentarii, 2024, 45(5): 1547-1554.

图/表 8

图1 CNTs的分散状态

Fig.1 Dispersion state of carbon nanotubes

表1 CNTs改性碳布/酚醛复合材料的层间性能

Table 1 Interlaminar properties of carbonnanotubes-modified carbon cloth/phenolic composites

CNTs 含量/%	层间剪切强度/MPa
0	40.8,34.4,32.1,36.0,47.4,19.7,29.5,36.0,33.3
0.5	39.8,32.7,41.4,32.1,37.5,35.2,38.9,40.6,41.4
1.0	39.3,59.8,42.9,44.6,42.8,39.7,32.8,44.7,43.6
1.5	88.4,47.2,63.7,49.1,40.5,93.1,37.4,61.9,42.1

表2 层间剪切强度的均值

Table 2 Average value of interlaminar shear strength

CNTs含量/%	层间剪切强度置信区间/MPa	平均值/MPa
0	(28.16119,40.54992)	33.55
0.5	(34.78935,40.667732)	37.35
1.0	(37.47845,49.23266)	42.51
1.5	(4138757,74.92354)	52.80

表3 CNTs改性定向碳纤维/酚醛复合材料的力学性能

Table 3 Mechanical properties ofcarbon nanotubes-modified oriented carbon fiber/penolic composites

CNTs 含量/%	弯曲弹性模量/GPa	弯曲强度/ GPa	层间剪切强度/MPa	无缺口冲击强度/(kJ·m^-2)
0	75.3	1.20	82.2	150
1.0	84.5	1.59	114	200
1.5	108.0	1.85	100	210
2.0	102.0	1.74	102	220
2.5	89.2	1.59	99.2	160

图2 CNTs含量为1.5%时分散体系的TEM图

Fig.2 Transmission electron microscopy image of dispersion system with 1.5% carbon nanotube content

图3 CNTs含量为2.5%时分散体系的TEM图

Fig.3 Transmission electron microscopy image of dispersion system with 2.5% carbon nanotube content

表4 CNTs改性玻璃纤维/酚醛复合材料的电阻率

Table 4 Resistivity of carbon nanotubes-modified glass fiber/phenolic composites

CNTs含量/%	电阻率/(Ω·m)
0	2.0×10¹⁰
1	4.0×10⁴
4	9.3×10^-1
5	8.0×10⁰
7	1.7×10^-1
8	1.6×10^-1
10	5.2×10^-2
12	4.6×10^-2
14	2.8×10^-2

图4 CNTs含量与复合材料导热系数之间的关系

Fig.4 Relationship between carbon nanotube content and thermal conductivity of composites

参考文献 25

[1]	刘涛, 曾黎明. 摩擦材料用改性酚醛树脂的研究进展[J]. 塑料科技, 2008, 36(12):84-89.
	LIU T, ZENG L M. Research progress of modified phenolic resin used for friction materials[J]. Plastics Science and Technology, 2008, 36(12):84-89. (in Chinese)
[2]	刘世强, 宁培森, 丁著明. 改性酚醛树脂的研究进展[J]. 热固性树脂, 2016, 31(5):64-70.
	LIU S Q, NING P S, DING Z M. Research progress in modified phenolic resin[J]. Thermosetting Resin, 2016, 31(5):64-70. (in Chinese)
[3]	马琛, 马壮, 高丽红, 等. 激光对鳞片石墨改性酚醛树脂涂层的损伤机理[J]. 中国光学, 2017, 10(2):249-255.
	MA C, MA Z, GAO L H, et al. Laser damage mechanism of flake graphite modified phenolic resin coating[J]. Chinese Optics, 2017, 10(2):249-255. (in Chinese)
[4]	于庆春, 万红. 片状石墨增强树脂基复合材料的耐激光烧蚀性能研究[J]. 无机材料学报, 2012, 27(2):157-161. doi: 10.3724/SP.J.1077.2012.00157
	YU Q C, WANG H. Ablation capability of flake graphite reinforced barium-phenolic resin composite underlong pulse laser irradiation[J]. Journal of Inorganic Materials, 2012, 27(2):157-161. (in Chinese)
[5]	李茂源, 卢林, 戴珍, 等. 玻璃微珠和ZrB₂改性石英酚醛复合材料的耐烧蚀性能[J]. 材料导报, 2019, 33(8):1302-1306.
	LI M Y, LU L, DAI Z, et al. Enhanced ablation resistance of glass beads and ZrB₂ modified SiO₂ (f)-phenolic composites[J]. Materials Review, 2019, 33(8):1302-1306. (in Chinese)
[6]	刘海龙, 黄玉东, 金苗苗, 等. 耐高温、低导热、韧性中空陶瓷微珠复合材料的制备及其性能[J]. 复合材料学报, 2022, 39(5):2378-2386.
	LIU H L, HUANG Y D, JIN M M, et al. Preparation and performance of hollow ceramic microsphere composites with high-temperature resistance, low thermal conductivity and toughness[J]. Acta Materiae Compositae Sinica, 2022, 39(5):2378-2386. (in Chinese)
[7]	姚亚琳, 刘晶, 王胖胖, 等. POSS改性热固性酚醛树脂的性能研究[J]. 复合材料科学与工程, 2022(5):92-97,119. doi: 10.19936/j.cnki.2096-8000.20220528.013
	YAO Y L, LIU J, WANG P P, et al. Study on effect of POSS on ablation properties of carbon/phenolic composite. Composites Scienceand Engineering, 2022(5):92-97,119. (in Chinese)
[8]	陈亚西, 陈平, 喻吉良, 等. ZrB₂颗粒改性碳/酚醛复合材料烧蚀隔热性能研究[C]//第四届高能束加工技术国际学术会议论文集. 青岛: 中国表面工程编辑部,2012:445-448.
	CHEN Y X, CHEN P, YU J L, et al. Ablation performance and insulation property of carbon/pheonlic composites with ZrB₂ particles[C]//Proceedings of the Fourth International Conference on High Energy Beam Processing Technology. Qingdao: China Surface Engineering,2012:445-448. (in Chinese)
[9]	魏化震, 李莹, 安振河. ZrB₂和POSS对碳布/酚醛复合材料烧蚀性能的影响[J]. 材料工程, 2014(11):38-42. doi: 10.11868/j.issn.1001-4381.2014.11.007
	WEI H Z, LI Y, AN Z H. Effect of ZrB₂ and POSS on ablation properties of carbon fabric/phenolic composite[J]. Materials Engineering, 2014(11):38-42. (in Chinese)
[10]	IIJIMA S I T. Single-shell carbon nanotubes of 1-nm diameter[J]. Nature, 1993, 363(17):603-605.
[11]	MUNIR K S, WEN C, LI Y. Carbon nanotubes and graphene as nanoreinforcements in metallic biomaterials: a review[J]. Advanced Biosystems, 2019, 3(3):1800212.
[12]	LUBINEAU G, RAHAMAN A. A review of strategies for improving the degradation properties of laminated continuous-fiber/epoxy composites with carbon-based nanoreinforcements[J]. Carbon, 2012, 50(7):2377-2395.
[13]	姚明远, 刘宁娟, 王嘉宁, 等. 功能化碳纳米管复合薄膜及其膜卷纱的电热性能[J]. 纺织学报, 2022, 43(5):86-91.
	YAO M Y, LIU N J, WANG J N, et al. Electrothermal properties of functionalization carbon nanotube composite films and films twisted yarns[J]. Journal of Textile Research, 2022, 43(5):86-91. (in Chinese)
[14]	师建军, 李弘瑜, 张凌东, 等. 烧蚀型防隔热/隐身多功能复合材料制备与性能[J]. 宇航材料工艺, 2021, 51(6):59-64.
	SHI J J, LI H Y, ZHANG L D, et al. Preparation and properties of multi-functional composite integrated with heat-shielding,insulating and radar-absorbing[J]. Aerospace Materials Technology, 2021, 51(6):59-64. (in Chinese)
[15]	刘琳, 宋静, 叶紫平, 等. 修饰碳纳米管对硼酚醛树脂基复合材料力学性能的影响[J]. 建筑材料学报, 2011, 14(5):610-614.
	LIU L, SONG J, YE Z P, et al. Effect of modified carbon nanotubes on mechanical properties of boron phenolic resin-based composite materials[J]. Journal of Building Materials, 2011, 14(5):610-614. (in Chinese)
[16]	刘毅佳, 滕会平, 郭亚林, 等. 纳米改性碳/酚醛树脂基复合材料性能研究[J]. 热固性树脂, 2008, 23(6):5-8.
	LIU Y J, TENG H P, GUO Y L, et al. Study on properties of carbon/phenolic resin composite modified by nanostuctured materials[J]. Thermosetting Resin, 2008, 23(6):5-8. (in Chinese)
[17]	陆晓芳, 陆雪萍, 王连军, 等. 碳纳米管/AgSbTe₂复合材料的制备及其热电性能[J]. 中国科技论文, 2022, 17(4):372-378.
	LU X F, LU X P, WANG L J, et al. Preparation and thermoelectric properties of CNTS/AgSbTe₂ composite material[J]. China Sciencepaper, 2022, 17(4):372-378. (in Chinese)
[18]	王春红, 赵玲, 白肃跃, 等. 改进Back Propagation神经网络预测麻纤维/UP复合材料的界面性能[J]. 复合材料学报, 2015, 32(6):1696-1702.
	WANG C H, ZHAO L, BAI S Y, et al. Prediction of interfacial properties of hemp fiber/UP composites by improved back propagation neural network[J]. Journal of Composites, 2015, 32(6):1696-1702. (in Chinese)
[19]	WU X S, CHEN X B, SONG H C. Effect of interface layer on strength of composite materials[J]. Journal of Composite Materials, 1987, 4(4):18-23.
[20]	ZHAO F. The effect of nano-component interface on the interfacial properties of carbon fiber/epoxy composites[D]. Harbin:Harbin University of Technology, 2011. (in Chinese)
[21]	OKPALUGO T, PAPAKONSTANTINOU P, MURPHY H, et al. High resolution XPS characterization of chemical functionalized MWCNTS and SWCNTS[J]. Carbon, 2005, 43(1):153-161.
[22]	ABIKO Y, HAYASAKI T, HIRAYAMA S, et al. Fabrication of organo.modified Carbon nanotube with excellent heat resistance and preparation of its polymer.based nano.composite by simple melt compounding[J]. Polymer Bulletin, 2021, 78(3):1585-1607.
[23]	JIA S K, YU D M, ZHU Y, et al. A feasible strategy to constructing hybrid conductive net works in PLA.based composites modified by CNT.d.RGO particles and PEG for mechanical and electrical properties[J]. Polymers for Advanced Technologies, 2020, 31(4):699-712.
[24]	贾汝锋, 尹保林, 张高鸿, 等. 聚四氟乙烯基电磁屏蔽复合膜的研制及特性研究[J]. 兵工学报, 2022, 43(11): 2916-2923.
	JIA R F, YIN B L, ZHANG G H, et al. Processing and characteristics of polytetrafluoroethylene based electromagnetic shielding composite films[J]. Acta Armamentarii, 2022, 43(11): 2916-2923. (in Chinese) doi: 10.12382/bgxb.2022.0594
[25]	饶早英, 王蜀霞, 牛君杰, 等. 碳纳米管的电学性质[J]. 重庆工学院学报(自然科学版), 2008, 22(1):52-54,121.
	RAO Z Y, WANG S X, NIU J J, et al. Electronic properties of carbon nanotubes[J]. Journal of Chongqing Institute of Technology(Nature Science), 2008, 22(1):52-54,121. (in Chinese)