三维网络填料增强聚合物基复合材料导热性能的研究进展

周正荣; 颜秀文; 何峰; 徐冬; 黄荣进; 李来风

doi:10.13801/j.cnki.fhclxb.20231208.001

三维网络填料增强聚合物基复合材料导热性能的研究进展

doi: 10.13801/j.cnki.fhclxb.20231208.001

周正荣^{1, 2},
颜秀文²,
何峰²,
徐冬¹,
黄荣进^{1, 3, ,},
李来风^{1, 3}

1.
中国科学院理化技术研究所　低温科学与技术重点实验室，北京 100190
2.
中国电子科技集团公司第四十八研究所(长沙半导体工艺设备研究所)，长沙 410111
3.
中国科学院大学　未来技术学院，北京 100049

基金项目: 中国科学院战略性先导科技专项(B类)(XDB25040300)；科技部智能传感器专项资助项目(2022YFB3207500)

详细信息

通讯作者:
黄荣进，博士，研究员，博士生导师，研究方向为低温材料物性与实验技术　E-mail: huangrongjin@mail.ipc.ac.cn

中图分类号: TB332
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- 文章访问数: 352
- HTML全文浏览量: 94
- PDF下载量: 28
- 被引次数: 0
出版历程
- 收稿日期: 2023-09-26
- 修回日期: 2023-11-19
- 录用日期: 2023-11-28
- 网络出版日期: 2023-12-09
- 刊出日期: 2024-07-15

Research progress on thermally conductive polymer matrix composites reinforced by three-dimensional network fillers

ZHOU Zhengrong^{1, 2},
YAN Xiuwen²,
HE Feng²,
XU Dong¹,
HUANG Rongjin^{1, 3
, ,},
LI Laifeng^{1, 3}

1.
Key Laboratory of Cryogenic Science and Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2.
The 48th Research Insititute of CETC, Changsha 410111, China
3.
School of Future Technology, University of Chinese Academy of Sciences, Beijing 100049, China

Funds: Strategic Priority Research Program of Chinese Academy of Sciences (XDB25040300); Smart Sensor Project Funded by the Ministry of Science and Technology, China (2022YFB3207500)

摘要

摘要: 聚合物在超导技术、航天航空、电子电路、动力电池、换热器等领域的应用十分广泛。随着器件的小型化、密集化和高功率，对于整体的散热要求越来越高，但是聚合物作为器件和设备粘接、封装等工艺的关键材料，热导率仅为0.2 W/(m∙K)，完全不能满足目前的散热需求，因此亟需提升聚合物的导热性能。由于在聚合物基体中构建连续的导热路径能极大提高聚合物的导热系数，往往能提高数倍或数十倍，因此采用三维网络填料增强聚合物导热性能是最为常用的一种方法之一。本文主要对用构建三维网络填料来增强高分子材料的导热性能的相关研究进行了整理，以制备方式的不同，将其归类为自组装法、相分离法、模板法、取向分布法等方法。最后，从制备方法的热导率提高值、可行性、稳定性等方面进行了总结分析，并对三维网络填料增强的聚合物基导热复合材料的未来发展前景进行了展望。
- 导热系数 /
- 复合材料 /
- 聚合物 /
- 三维网络增强 /
- 无机填料
Abstract: Polymer materials find wide applications in various fields such as superconducting technology, aerospace, electronic circuits, power batteries, heat exchangers, among others. With the increasing demands for miniaturization, densification, and high power of devices, the overall heat dissipation requirements have escalated. However, polymers, serving as crucial materials in device encapsulation and bonding processes, exhibit a low thermal conductivity of only 0.2 W/(m∙K), which falls significantly short of current heat dissipation needs. Therefore, there is an urgent need to enhance the thermal conductivity of polymers. Constructing continuous thermal pathways within the polymer matrix has been shown to significantly improve the thermal conductivity, often increasing it several times or even tens of times. Hence, utilizing three-dimensional network fillers to reinforce the thermal conductivity of polymers stands out as one of the most commonly employed methods. Accordingly, this paper organizes relevant studies on enhancing the thermal conductivity of polymeric materials through the construction of three-dimensional network fillers. Based on different preparation methods, these are categorized into self-assembly, phase-separation, template-methods, oriented-distribution methods, among others. Finally, a summary analysis is provided from aspects such as the increase in thermal conductivity values due to preparation methods, feasibility, stability, and prospects for the future development of polymer-based thermally conductive composites reinforced by three-dimensional network fillers.
- thermal conductivity /
- composites /
- polymer /
- 3-dimensional reinforcement /
- inorganic filler

HTML全文

图 1 石墨烯复合泡沫(GHFs)/环氧树脂(EP)合成方案及其热导率^[82]

Figure 1. Preparation and thermal conductivity of graphene hybrid foams (GHFs)/epoxy resin (EP) composites^[82]

GO—Graphene oxide; GNP—Graphene nanoplatelets

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图 2 反应诱导相分离法制备环氧树脂复合材料^[88]

Figure 2. Preparation of epoxy resin composites by the reaction-induced phase separation method^[88]

BNNSs—Boron nitride nanosheets; PEI—Polyetherimide; DGEBA—Diglycidyl ether of bisphenol A

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图 3 BN/聚丙烯(PP)纤维(PF)复合材料的制备流程^[89]

Figure 3. Preparation process of BN/polypropylene (PP) fiber (PF) composites^[89]

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图 4 热压法制备三元复合材料^[90]

Figure 4. Preparation of ternary composites by hot pressing^[90]

DMF—N, N-dimethylformamide

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图 5 聚偏氟乙烯(PVDF)@多壁碳纳米管(MWCNT)/BN复合材料的制备流程^[91]

Figure 5. Preparation of poly(vinylidene fluoride) (PVDF)@multi-wall carbon nanotube (MWCNT)/BN composites^[91]

WVIPS—Water vapor induced phase separation

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图 6 冰模板法和浸渍法相结合制备三维有序氮化硼(3D-BN)/EP复合材料^[52]

Figure 6. Preparation of ordered three-dimensional boron nitride (3D-BN)/EP composites by the combination of ice-template method and impregnation^[52]

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图 7 利用盐模板法和浸渍法制备EP复合材料^[94]

Figure 7. Preparation of EP composites by salt-template method and impregnation^[94]

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图 8 3D打印技术制备高导热性能的石墨烯/热塑性聚氨酯(TPU)复合材料^[96]

Figure 8. Graphene/thermoplastic polyurethane (TPU) composites with high thermal conductivity prepared by 3D printing technology^[96]

w—Width of the deposited filament; h—Height of the deposited filament; v—Printing head velocity

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图 9 蛋白质发泡和浸渍技术制备3D-Al₂O₃/EP复合材料^[99]

Figure 9. 3D-Al₂O₃/EP composites prepared by protein foaming and impregnation^[99]

PVA—Polyvinyl alcohol; f-Al₂O₃—Al₂O₃ framework

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图 10 以三聚氰胺骨架为模板制备了三聚氰胺泡沫(MF)@Cu/聚乙二醇(PEG)复合材料^[101]

Figure 10. Melamine foam (MF)@Cu/polyethylene glycol (PEG) composites prepared with melamine framework as a template^[101]

PCM—Phase change material

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图 11 以多孔Ni泡沫为模板制备了三维石墨烯网络(3D GF)/EP复合材料^[102]

Figure 11. Three-dimensional graphene fillers (3D GF)/EP composites prepared with porous Ni foam as a template^[102]

CVD—Chemical vapor deposition

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图 12 模板法和浸渍法制备碳化硅纳米线(SiC_w)/EP复合材料^[103]

Figure 12. Preparation of silicon carbide nanowires (SiC_w)/EP composites by template method and impregnation^[103]

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图 13 通过模板法制备Al₂O₃/四足状氧化锌晶须(T-ZnO_w)/EP复合材料^[104]

Figure 13. Al₂O₃/tetrapod-like zinc oxide whiskers (T-ZnO_w)/EP composites prepared by the template method^[104]

RPCs—Reticulated porous alumina ceramics

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图 14 以碳毡为骨架所制备的Cu-Felt/Epoxy复合材料及其热导率^[105]

Figure 14. Thermal conductivity of Cu-Felt/Epoxy composites prepared with carbon Felt as a skeleton^[105]

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图 15 以三维还原氧化石墨烯(rGO)泡沫材料为模板制备的3D-SiC^[107]

Figure 15. Preparation of 3D-SiC using 3D Reduced GO (rGO) foam as a template^[107]

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图 16 通过模板辅助法制备碳纤维气凝胶(CFA)/EP和SiC@CFA/EP复合材料^[108]

Figure 16. Carbon fiber aerogel (CFA)/EP and SiC@CFA/EP composites prepared by the template-assisted method^[108]

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图 17 利用棉花糖做模板制备3D-Al₂O₃/EP复合材料^[109]

Figure 17. Preparation of 3D-Al₂O₃/EP composites using cotton candy as a template^[109]

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图 18 通过抽滤法制备高热导率的环氧树脂基复合材料^[110]

Figure 18. Preparation of EP matrix composites with high thermal conductivity by the filtration method^[110]

BNO—Oxide hBN; f-BNNS—Functionalized BNNS

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图 19 通过真空抽滤法制备高热导率的hBN/EP复合材料^[111]

Figure 19. The hBN/EP composites with high thermal conductivity prepared by vacuum extraction and filtration^[111]

H—

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图 20 通过定向冷冻制备高热导BNNS/EP复合材料^[58]

Figure 20. Preparation of high thermal conductivity BNNS/EP composites by directional freezing^[58]

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图 21 通过磁性排列和定向冷冻法制备高热导纳米碳纤维(CNFs)/硅橡胶(SR)复合材料^[114]

Figure 21. Carbon nanofibers (CNFs)/silicone rubber (SR) composites with high thermal conductivity prepared by magnetic alignment and directional freezing^[114]

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表 1 室温下部分聚合物的导热系数^{[7, 14-17]}

Table 1. Thermal conductivity of some polymers at room temperature^{[7, 14-17]}

Material	Thermal conductivity/ (W·(m∙K)⁻¹)
Low-density polyethylene (LDPE)	0.33
Polypropylene (PP)	0.14
Polystyrene (PS)	0.04-0.14
Polyethylene terephthalate (PET)	0.29
Polymethyl methacrylate (PMMA)	0.15-0.25
Polytetrafluoroethylene (PTFE)	0.25
Polyvinyl chloride (PVC)	0.12-0.17
Polyetheretherketone (PEEK)	0.25
Polycarbonate (PC)	0.19
Polybutylene terephthalate (PBT)	0.25
Polysulfone (PSU)	0.22
Polyvinylidene difluoride (PVDF)	0.19
Thermoplastic polyimide (TPI)	0.1
Epoxy (EP)	0.17-0.21
Nylon 6, 6	0.25
Urethane base thermoplastic elastomer (TPU)	0.19
Poly(dimethylsiloxane) (PDMS)	0.25

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表 2 室温下部分金属与碳纳米管、碳纤维、石墨、石墨烯的导热系数^{[10, 16-17, 36, 44-46]}

Table 2. Thermal conductivity of some metals and carbon nanotubes, carbon fiber, graphite, and graphene at room temperature^{[10, 16-17, 36, 44-46]}

Material	Thermal conductivity/(W·(m∙K)⁻¹))
Gold	345
Silver	450
Copper	483
Nickle	158
Aluminum	204
Tungsten	142
Carbon nanotubes	1000-4000
Carbon fibers	300-1000
Graphene	2000-6000
Graphite	100-400

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表 3 常温下部分导热填料的导热系数^{[10, 16-17, 36, 44-46]}

Table 3. Thermal conductivities of some thermally conductive fillers at room temperature^{[10, 16-17, 36, 44-46]}

Material	Thermal conductivity/ (W·(m∙K)⁻¹)
Silicon nitride (Si₃N₄)	103-200
Boron nitride (BN)	29-300
Hexagonal boron nitride (hBN)	185-300
Aluminum nitride (AlN)	100-300
Silicon carbide (SiC)	120-611
Alumina (Al₂O₃)	20-29
Zinc oxide (ZnO)	60
Beryllium oxide (BeO)	260
Magnesium oxide (MgO)	25-30
Diamond	2000

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表 4 不同方法所制备的导热填料三维网络增强聚合物基复合材料汇总表

Table 4. Summary of three-dimensional network reinforced polymer matrix composites prepared by different methods

Preparation method	Filler	Matrix	Filling rate	Thermal conductivity/ (W∙(m∙K)⁻¹)	Notes
Self-assembly method	Graphene^[82]	Epoxy	19wt%	35.5	Thermal reduction
Self-assembly method	Graphene/SiC nanowires^[83]	Epoxy	0.092vol%	0.64	Thermal reduction
Phase-separation method	Graphene^[86]	Epoxy/PES	10wt%	0.71	Reaction induced phase separation
	hBN^[87]	Epoxy/PES	10wt%	0.52
	BNNS-NH₂^[88]	Epoxy/PEI	1wt%	0.37
	hBN^[89]	PP/PS	50wt%	5.57	Hot pressing
Template method	BNNS^[92]	Epoxy	9.29vol%	2.85	Ice-template
	hBN^[94]	PVDF	21wt%	1.23	Salt-template
	Hollow BN microbeads^[95]	Epoxy	65.6vol%	17.61	Salt-template
	Al₂O₃^[99]	Epoxy	23.32vol%	2.58	Foam-template
	BNNS/melamine^[100]	Epoxy	1.1vol%	0.6
	Graphene^[102]	Epoxy	0.14vol%	0.52
	SiC nanowires^[103]	Epoxy	3.91vol%	0.43	Polymer removal
	Al₂O₃/T-ZnO_w^[104]	Epoxy	17.7vol%	1.97	Polymer removal
	C felt/Cu^[105]	Epoxy	29.34vol%	30.69	Template conversion
	SiC^[106]	Epoxy	6.52vol%	10.26
	Cotton candy/Al₂O₃^[109]	Epoxy	36.20vol%	3.17
Orientation-distribution method	SiC nanowires/f-BNNS^[110]	Epoxy	21.9vol%	4.22	Vacuum filtration
	BNMS^[111]	Epoxy	44vol%	9	Vacuum filtration
	BNNS^[58]	Epoxy	15vol%	6.07	Bidirectional freezing
Notes: PES—Polyethersulfone; BNMS—

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