Abstract
To meet the requirements of spacecraft for the thermal conductivity of resins and solve the problem of low thermal conduction efficiency when 3D printing complex parts, we propose a new type of continuous mesophase-pitch-based carbon fiber/thermoplastic polyurethane/epoxy (CMPCF/TPU/epoxy) composite filament and its preparation process in this study. The composite filament is based on the high thermal conductivity of CMPCF, the high elasticity of TPU, and the high-temperature resistance of epoxy. The tensile strength and thermal conductivity of the CMPCF/TPU/epoxy composite filament were tested. The CMPCF/TPU/epoxy composites are formed by 3D printing technology, and the composite filament is laid according to the direction of heat conduction so that the printed part can meet the needs of directional heat conduction. The experimental results show that the thermal conductivity of the printed sample is 40.549 W/(m·K), which is 160 times that of pure epoxy resin (0.254 W/(m·K)). It is also approximately 13 times better than that of polyacrylonitrile carbon fiber/epoxy (PAN-CF/epoxy) composites. This study breaks through the technical bottleneck of poor printability of CMPCF. It provides a new method for achieving directional thermal conductivity printing, which is important for the development of complex high-performance thermal conductivity products.
概要
目的
为满足航天器对树脂导热性能的要求, 解决3D 打印复杂零件时导热效率低的问题, 本研究提出一种新型连续 中间相沥青基碳纤维/热塑性聚氨酯/环氧树脂(CMPCF/TPU/epoxy)复合长丝并介绍其制备工艺。
创新点
1. 该复合长丝的制备基于连续中间相沥青基碳纤维(CMPCF)的高导热性能、热塑性聚氨酯(TPU)的高弹 性和环氧树脂(epoxy)的耐高温性能。2. 沿导热方向打印长丝, 并提出热固性复合丝材打印件的新固化方式。
方法
1. 采用上浆剂法进行表面上浆, 选取水溶性聚氨酯作为表面上浆剂, 提升连续中间相沥青基碳纤维聚束性。2. 通过增韧预处理, 选取TPU 作为增韧基体材料, 在上浆后的碳纤维束外包裹一层具有高韧性高强度的树脂层。 3. 采用浸涂处理工艺, 选取固态环氧树脂, 成功制备出高导热CMPCF/TPU/epoxy 复合丝材。4. 沿导热方向规 划打印路径并进行打印测试, 验证复合长丝的可打印性和打印件的导热系数。
结论
1. 通过对CMPCF 进行表面上浆、增韧预处理和预浸处理, 成功制备出高导热性能的CMPCF/TPU/epoxy 复合 长丝; 在CMPCF 外包裹TPU, 解决了CMPCF 因脆性而难以打印的问题。2. 3D 打印使纤维沿导热方向铺设, 为制备具有高导热系数的复杂打印件提供了一种新方法。3. 导热系数测试表明, 当CMPCF 体积含量仅为6.6% 时, 复合材料的导热系数为40.549 W/(m·K), 是纯环氧树脂的160 倍, 是聚丙烯腈基碳纤维(PAN-CF)体积 为14.6%时复合材料的13 倍, 因此CMPCF 的加入明显提高了打印件的导热性能。
References
ASTM (American Society for Testing and Materials), 2017. Standard Test Methods for Properties of Continuous Filament Carbon and Graphite Fiber Tows, ASTM D4018-17. American Society for Testing and Materials, USA.
Dong KX, Sheng N, Zou DQ, et al., 2020. A high-thermal-conductivity, high-durability phase-change composite using a carbon fibre sheet as a supporting matrix. Applied Energy, 264:114685. https://doi.org/10.1016/j.apenergy.2020.114685
Fan BH, Liu Y, He DL, et al., 2017. Enhanced thermal conductivity for mesophase pitch-based carbon fiber/modified boron nitride/epoxy composites. Polymer, 122:71–76. https://doi.org/10.1016/j.polymer.2017.06.060
Garimella SV, Persoons T, Weibel JA, et al., 2017. Electronics thermal management in information and communications technologies: challenges and future directions. IEEE Transactions on Components, Packaging and Manufacturing Technology, 7(8):1191–1205. https://doi.org/10.1109/tcpmt.2016.2603600
Guo HC, Zhao HY, Niu HY, et al., 2021. Highly thermally conductive 3D printed graphene filled polymer composites for scalable thermal management applications. ACS Nano, 15(4):6917–6928. https://doi.org/10.1021/acsnano.0c10768
Guo LC, Zhang ZY, Li MH, et al., 2020. Extremely high thermal conductivity of carbon fiber/epoxy with synergistic effect of MXenes by freeze-drying. Composites Communications, 19:134–141. https://doi.org/10.1016/j.coco.2020.03.009
Hu JT, Huang Y, Yao YM, et al., 2017. Polymer composite with improved thermal conductivity by constructing a hierarchically ordered three-dimensional interconnected network of BN. ACS Applied Materials & Interfaces, 9(15): 13544–13553. https://doi.org/10.1021/acsami.7b02410
Isarn I, Bonnaud L, Massagués L, et al., 2020. Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites. Polymer International, 69(3):280–290. https://doi.org/10.1002/pi.5949
Ji JC, Chiang SW, Liu MJ, et al., 2020. Enhanced thermal conductivity of alumina and carbon fibre filled composites by 3-D printing. Thermochimica Acta, 690:178649. https://doi.org/10.1016/j.tca.2020.178649
Liu JC, Li WW, Guo YF, et al., 2019. Improved thermal conductivity of thermoplastic polyurethane via aligned boron nitride platelets assisted by 3D printing. Composites Part A: Applied Science and Manufacturing, 120:140–146. https://doi.org/10.1016/j.compositesa.2019.02.026
Ma C, Ma Z, Gao LH, et al., 2018. Preparation and characterization of coatings with anisotropic thermal conductivity. Materials & Design, 160:1273–1280. https://doi.org/10.1016/j.matdes.2018.10.046
Ma JK, Shang TY, Ren LL, et al., 2020. Through-plane assembly of carbon fibers into 3D skeleton achieving enhanced thermal conductivity of a thermal interface material. Chemical Engineering Journal, 380:122550. https://doi.org/10.1016/j.cej.2019.122550
Ming YK, Wang B, Zhou J, et al., 2021. Performance and applications of 3D printed continuous fiber-reinforced thermosetting composites. Aeronautical Manufacturing Technology, 64(15):58–65 (in Chinese). https://doi.org/10.16080/j.issn1671-833x.2021.15.058
Miranda AT, Bolzoni L, Barekar N, et al., 2018. Processing, structure and thermal conductivity correlation in carbon fibre reinforced aluminium metal matrix composites. Materials & Design, 156:329–339. https://doi.org/10.1016/j.matdes.2018.06.059
Mun SY, Lim HM, Lee DJ, 2015. Thermal conductivity of a silicon carbide/pitch-based carbon fiber-epoxy composite. Thermochimica Acta, 619:16–19. https://doi.org/10.1016/j.tca.2015.09.020
Na TY, Liu X, Jiang H, et al., 2018. Enhanced thermal conductivity of fluorinated epoxy resins by incorporating inorganic filler. Reactive and Functional Polymers, 128: 84–90. https://doi.org/10.1016/j.reactfunctpolym.2018.05.004
Oh H, Kim Y, Kim J, 2019. Co-curable poly (glycidyl methacrylate)-grafted graphene/epoxy composite for thermal conductivity enhancement. Polymer, 183:121834. https://doi.org/10.1016/j.polymer.2019.121834
Stepashkin AA, Chukov DI, Senatov FS, et al., 2018. 3D-printed PEEK-carbon fiber (CF) composites: structure and thermal properties. Composites Science and Technology, 164: 319–326. https://doi.org/10.1016/j.compscitech.2018.05.032
Tang B, Yi M, Liang YM, et al., 2020. Preparation and study on the thermal conductivity of high thermal conductivity pitch based carbon fiber/epoxy composite. China Plastics Industry, 48(8):157–160 (in Chinese).
Tarhini AA, Tehrani-Bagha AR, 2019. Graphene-based polymer composite films with enhanced mechanical properties and ultra-high in-plane thermal conductivity. Composites Science and Technology, 184:107797. https://doi.org/10.1016/j.compscitech.2019.107797
Tong YL, Tao ZC, Li YF, et al., 2022. Carbon materials with high thermal conductivity and its application in spacecraft. Chinese Space Science and Technology, 42(1):131–138 (in Chinese). https://doi.org/10.16708/j.cnki.1000-758X.2022.0015
Watts R, Kistner M, Colleary A, 2006. Materials opportunity to electronic composite enclosures for aerospace and spacecraft thermal management. American Institute of Physics, 813(1):19–26. https://doi.org/10.1063/1.2169175
Wu B, Li JJ, Li X, et al., 2021. Gravity driven ice-templated oriental arrangement of functional carbon fibers for high in-plane thermal conductivity. Composites Part A: Applied Science and Manufacturing, 150:106623. https://doi.org/10.1016/j.compositesa.2021.106623
Wu WF, Liu N, Cheng WL, et al., 2013. Study on the effect of shape-stabilized phase change materials on spacecraft thermal control in extreme thermal environment. Energy Conversion and Management, 69:174–180. https://doi.org/10.1016/j.enconman.2013.01.025
Xiao C, Tang YL, Chen L, et al., 2019. Preparation of highly thermally conductive epoxy resin composites via hollow boron nitride microbeads with segregated structure. Composites Part A: Applied Science and Manufacturing, 121: 330–340. https://doi.org/10.1016/j.compositesa.2019.03.044
Xiao WK, Luo XJ, Ma PF, et al., 2018. Structure factors of carbon nanotubes on the thermal conductivity of carbon nanotube/epoxy composites. AIP Advances, 8(3):035107. https://doi.org/10.1063/1.5017784
Xue F, Han X, Sun DH, 2015. The application of 3D printing technology in space composites manufacturing. Spacecraft Recovery & Remote Sensing, 36(2):77–82 (in Chinese). https://doi.org/10.3969/j.issn.1009-8518.2015.02.011
Yang W, Huo HL, Li HB, et al., 2020. Research progress of multifunctional thermal control materials and structures of aerospace vehicles. Structure & Environment Engineering, 47(2): 1–12 (in Chinese). https://doi.org/10.19447/j.cnki.11-1773/v.2020.02.001
Zheng XR, Kim S, Park CW, 2019. Enhancement of thermal conductivity of carbon fiber-reinforced polymer composite with copper and boron nitride particles. Composites Part A: Applied Science and Manufacturing, 121:449–456. https://doi.org/10.1016/j.compositesa.2019.03.030
Zhu CY, Chen ZH, Zhu RJ, et al., 2021. Vertically aligned Al2O3 fiber framework leading to anisotropically enhanced thermal conductivity of epoxy composites. Advanced Engineering Materials, 23(9):2100327. https://doi.org/10.1002/adem.202100327
Acknowledgments
This work is supported by the National Natural Science Foundation of China (Nos. 52175474 and 52275498).
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Haiguang ZHANG designed the research. Kunlong ZHAO and Haiguang ZHANG processed the corresponding data. Kunlong ZHAO wrote the first draft of the manuscript. Qingxi HU and Jinhe WANG helped to organize the manuscript. Kunlong ZHAO and Haiguang ZHANG revised and edited the final version.
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Haiguang ZHANG, Kunlong ZHAO, Qingxi HU, and Jinhe WANG declare that they have no conflict of interest.
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Zhang, H., Zhao, K., Hu, Q. et al. Preparation and 3D printing of high-thermal-conductivity continuous mesophase-pitch-based carbon fiber/epoxy composites. J. Zhejiang Univ. Sci. A 24, 162–172 (2023). https://doi.org/10.1631/jzus.A2200413
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DOI: https://doi.org/10.1631/jzus.A2200413
Key words
- Thermal conductivity
- 3D printing
- Continuous mesophase-pitch-based carbon fiber (CMPCF)
- Thermoplastic polyurethane (TPU)
- Epoxy composite filament