Research progress of thermally conductive polymer composites with three-dimensional interconnected network structures
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摘要: 热界面材料可以有效地将高温电子器件的热量快速传递到热管理元件,以缓解电子器件过热而导致的元件寿命恶化的问题。近年来,由聚合物和高导热填料制成的聚合物基复合材料因其密度低、导热性能可调而受到广泛关注。不同于传统的填料随机分散的复合材料,在聚合物基体中构建三维连续网络结构可以显著增加填料/填料接触、降低导热渗透阈值和界面热阻,显著改善复合材料的导热性能。首先,简要分析了聚合物基导热复合材料的导热机制。其次,总结了具有连续网络结构的聚合物基导热复合材料的构筑工艺,主要包括基于三维导热填料网络的预构筑、基于聚合物颗粒/粉末的后加工、基于聚合物纤维/织物的后加工、基于聚合物胶乳的铸膜或絮凝等工艺。再次,系统总结了不同类型的导热填料对聚合物复合材料导热性能的影响,主要包括金属填料、陶瓷填料、碳基填料及其混杂填料等。最后,对具有三维连续网络结构的聚合物基导热复合材料的发展前景进行了展望。Abstract: Thermal interface materials could effectively transfer the heat from electronic devices with high temperature to the thermal management components, so as to alleviate the problems of deterioration of component life caused by overheating of electronic devices. In recent years, the polymer-based composites composed of polymer matrix and reinforcing fillers with high thermal conductivities have been widely concerned because of their low density and adjustable thermal conductivities. Different from the conventional composites with randomly dispersed fillers, the construction of three-dimensional (3D) continuous network structure in the polymer matrix could significantly increase the filler/filler contact, reduce the percolation threshold of thermal conductivity and the interfacial thermal resistance, and then significantly improve the thermal conductivities of composites. Firstly, the thermal conductivity mechanisms of polymer-based thermal conductive composites were briefly analyzed. Secondly, the construction processes of polymer-based thermally conductive composites with interconnected network structures were summarized, mainly including the pre-construction of 3D thermally conductive filler network, the post-processing based on polymer particle/powder, the post-processing based on polymer fiber/fabric, and the film casting or flocculation based on polymer latex. The effects of different types of thermal conductive fillers on the thermal conductivities of polymer composites were summarized, mainly including metal fillers, ceramic fillers, carbon-based fillers and their hybrid fillers. Finally, the development prospects of polymer-based thermally conductive composites with interconnected network structures were prospected.
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图 2 (a) 流化床化学气相沉积(CVD)工艺制备氮化硼纳米粒子(BNNS)/碳纳米管(CNTs)示意图和三维BNNS/CNTs/环氧树脂(EP)复合材料制备示意图;(b) 三维泡沫骨架上沉积的BNNS/CNTs的SEM图像;(c) 三维导热网络结构对BNNS/CNTs/EP复合材料导热系数的增强作用[39]
Figure 2. (a) Schematic illustration of the fluidized bed chemical vapor deposition (CVD) process for the fabrication of boron nitride nanoparticles (BNNS)/carbon nanotubes (CNTs) and the preparation process of 3D BNNS/CNTs/epoxy (EP) composie; (b) SEM image of BNNS/CNTs deposited on 3D foam skeleton; (c) Enhancement of 3D network structure on thermal conductivity of BNNS/CNTs/EP composite[39]
PU—Polyurethane; CNTs15%—Mass fraction (15wt%) of CNTs in BNNS/CNTs samples
图 3 (a) 具有连续网络结构的(CNT+BN)@聚偏二氟乙烯(PVDF)复合材料制备示意图;(b) 均匀分散的CNT/BN/PVDF复合材料和具有连续网络结构的(CNT+BN)@PVDF复合材料在不同混杂填料配比下的导热系数的对比; (c) (CNT+BN)@PVDF复合材料在不同热压温度下的导热系数变化,插图显示了混杂填料网络形貌[18]
Figure 3. (a) Schematic representation showing the preparation of interconnected (CNT+BN)@polyvinylidene fluoride (PVDF) composites; (b) Thermal conductivities of uniformly dispersed CNT/BN/PVDF and interconnected (CNT+BN)@PVDF composites as a function of the volume ratio of hybrid fillers; (c) Thermal conductivities of (CNT+BN)@PVDF composites molded at varied compression temperature, the insets exhibited the morphologies of hybrid filler network[18]
TC—Thermal conductivity
图 4 (a) 热塑性聚氨酯(TPU)/聚多巴胺(PDA)/Ag复合材料制备示意图;(b) TPU/PDA/Ag纤维膜表面 SEM图像;(c) 热流沿面内方向的连续Ag粒子路径的传导示意图;(d) 不同Ag含量下TPU/PDA/Ag复合膜的导热系数[53]
Figure 4. (a) Schematic illustration of the preparation process of thermoplastic polyurethane (TPU)/polydopamine (PDA)/Ag composites; (b) SEM image of the surface of TPU/PDA/Ag fiber membrane; (c) Schematic illustration of heat flow transfer along continuous silver particles pathways in-plane direction; (d) Thermal conductivities of TPU/PDA/Ag composite films versus mass fraction of Ag[53]
TPU/PDA/Ag-x—Mass fraction (xwt%) of Ag loading in TPU/PDA/Ag (polyurethane/polydopamine/argentum) composite films
图 5 (a) 通过胶乳共混-铸膜工艺制备具有连续网络的天然橡胶(NR)-羧基化多壁碳纳米管(MWCNTR)复合材料的制备示意图;(b) NR-MWCNTR复合材料的TEM图像[56]
Figure 5. (a) Schematic representation of the preparation of natural rubber (NR)-carboxylated multi-walled carbon nanotubes (MWCNTR) composites with interconnected network by latex blending-solution casting process; (b) TEM images of NR-MWCNTR composite film[56]
MWCNT—Multi-walled carbon nanotube
图 6 聚合物和导热填料(包括金属填料、碳基填料和陶瓷填料)的导热系数[10]
Figure 6. Thermal conductivity of common materials including polymers and fillers (Metals, ceramics and carbon materials)[10]
BNNT—Boron nitride nanotube; h-BN—Hexagonal boron nitride; BAs—Cubic boron arsenide; AlN—Aluminum nitride; BNNS—Boron nitride nanosheet
图 7 (a) Cu@TPU复合材料制备和Cu2+在TPU颗粒表面还原的示意图[71];(b) PVDF@PDA@Ag/低熔点合金(LMPA)、PVDF/LMPA和PVDF@PDA/LMPA复合材料制备示意图[74]
Figure 7. (a) Schematic illustration of preparation process of Cu@TPU composites and Cu2+ reduction process on TPU granules[71]; (b) Schematic diagram of fabrication process of PVDF@PDA@Ag/low melting point alloy (LMPA), PVDF/LMPA and PVDF@PDA/LMPA composites[74]
图 8 (a) BN@聚苯硫醚(PPS)和BN/PPS复合材料的制备示意图;(b) 30vol%BN含量下BN@PPS颗粒的OM图像;(c) 具有连续网络结构的BN/PPS复合材料和PPS/BN共混复合材料的导热系数[85]
Figure 8. (a) Schematic illustrating the synthesis process of BN@polyphenylene sulfide (PPS) and BN/PPS composite; (b) OM image of BN@PPS particles with 30vol%BN loading; (c) Thermal conductivity of the interconnected architecture BN/PPS composites and PPS/BN blend composites[85]
APTES—3-aminopropyltriethoxysilane; S-PPS—Segregated polyphenylene sulfide; A-BN—APTES functionalized BN; PEI—Polyethylenimine
图 9 (a) 具有连续网络结构的还原氧化石墨烯(RGO)/TPU复合材料的制备过程示意图;(b) RGO/TPU复合材料切片的OM图像;(c) 连续网络结构RGO/TPU的导热系数[20]
Figure 9. (a) Schematic illustration of fabrication process of reduced graphene oxide (RGO)/TPU composite with interconnected structure; (b) Optical microscope images of RGO/TPU composite sections; (c) Thermal conductivities of RGO/TPU with interconnected structure[20]
GO—Graphene oxide
图 10 (a) 具有三维连续网络结构的聚苯乙烯(PS)/氧化石墨烯(GO)-PDA复合材料制备示意图,插图为PS/GO-PDA薄膜照片;((b), (b’)) PS/GO-PDA微球的SEM图像;(c) 不同填料含量下PS/GO-PDA复合材料的面内和面外导热系数;(d) 不同填料含量下PS/GO和PS/GO-PDA体积电阻率[103]
Figure 10. (a) Schematic illustration of preparation of the polystyrene (PS)/graphene oxide (GO)-PDA composites with a continuous three-dimensional network. Inset: photograph of the PS/GO-PDA thin film; ((b), (b’)) SEM images of the PS/GO-PDA microspheres; (c) In-plane and through-plane thermal conductivities of the PS/GO-PDA composites with different filler loadings; (d) Volume electrical resistivity of the PS/GO and PS/GO-PDA with different filler loadings[103]
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