Preparation and properties of hexagonal boron nitride/semi-aromatic polyamide 12T composites with high-temperature resistance and high thermal conductivity prepared by mixed solvent dispersion method
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摘要: 制备兼具优异耐高温性能和导热性能的聚合物基复合材料对于电子元器件的封装保护、高效散热和稳定成型至关重要。本文通过混合溶剂分散法(MSD)制备了六方氮化硼(BN)/半芳香聚酰胺12T (PA12T)复合材料，并对复合材料的微观结构、导热、耐高温、介电和力学性能进行了表征。结果表明：混合溶剂分散法可以有效实现BN和PA12T粉末的均匀悬浮，并可协同真空辅助自组装法与真空热压法构筑具有均一分散和取向结构的复合材料。研究表明，当BN/PA12T复合材料中的BN含量为40wt%时，混合溶剂分散法制备的样品的平面导热率可以达到2.73 W/(m·K)，是机械混合法(MM)制备的样品(1.59 W/(m·K))的1.72倍，同时其具有优异的力学性能、低介电常数(3.6)、介电损耗(0.016)和显著的耐高温性能(维卡软化点超过250℃且初始分解温度可达446℃)。综上所述，混合溶剂分散法制备的BN/PA12T复合材料在电子封装及热管理领域中具有广阔的应用前景。Abstract: Fabrication of the polymer-based composites with excellent high temperature resistance and thermal conductivity is very important for the packaging protection, efficient heat dissipation and processing of electronic components. In this work, high temperature resistant and thermally conductive hexagonal boron nitride (BN)/semi-aromatic polyamide 12T (PA12T) composites with uniform dispersion and orientation filler structure were prepared by mixed solvent dispersion (MSD) method, and the microstructure, thermal conductivity, high-temperature resistance, dielectric and mechanical properties of the composites were systematically characterized. The results show that the BN powder and PA12T powder can be suspended uniformly in the mixed solvent. Next, combining the vacuum-assisted self-assembly technique and vacuum hot compression method, the composites with uniformly dispersed and oriented BN structure are fabricated successfully. When the content of BN is 40wt% in BN/PA12T composite, the in-plane thermal conductivity of the composite prepared by the MSD method is 2.73 W/(m·K), which is 1.72 times that of the composite (1.59 W/(m·K)) prepared by the mechanical mixing (MM) method. Furthermore, the composite prepared by the MSD method also possesses excellent mechanical properties, low dielectric permittivity of 3.6 and dielectric loss of 0.016, outstanding high-temperature resistance with the initial decomposition temperature of 446℃ and Vicat softening temperature of more than 250℃. Therefore, the BN/PA12T composite prepared by the MSD method will have a wide range of applications in the fields of electronic packaging and thermal management.
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图 1 六方氮化硼(BN)和半芳香聚酰胺12T (PA12T)粉末悬浮于不同溶剂和混合溶剂(a)及不同静置时间的40wt%BN/PA12T混合粉末悬浮于混合溶剂(b)的光学图像
Figure 1. Images of hexagonal boron nitride (BN) and semi-aromatic polyamide 12T (PA12T) powder suspended in different solvents and mixed solvent (a) and 40wt%BN/PA12T mixed powder suspended in mixed solvent with different resting time (b)
图 2 BN (a)、PA12T (b) 及机械混合法(MM) ((c), (e), (g), (i))和混合溶剂分散法(MSD) ((d), (f), (h), (j))制备BN/PA12T复合材料的SEM图像
Figure 2. SEM images of BN powder (a) and pure PA12T (b), the composites prepared by mechanical mixing (MM) method ((c), (e), (g), (i)) and mixed solvent dispersion (MSD) method ((d), (f), (h), (j))
图 3 不同方法制备的BN/PA12T复合材料的XRD图谱
Figure 3. XRD patterns of the BN/PA12T composites prepared by different methods
图 4 不同方法制备的BN/PA12T复合材料沿平面方向和厚度方向的导热率(a)及各项异性指数(b)
Figure 4. Thermal conductivities (a) along the in-plane and through-plane directions and anisotropy index (b) of the BN/PA12T composites prepared by different methods
图 5 机械混合法(A)和混合溶剂分散法(B)制备的40wt%BN/PA12T复合材料在LED热管理应用过程中的热成像图
Figure 5. Optical and thermal images of the 40wt%BN/PA12T composites prepared by the mechanical mixing method (A) and the mixed solvent dispersion method (B) for the thermal management of LED
图 6 不同方法制备的BN/PA12T复合材料的储能模量
Figure 6. Storage modulus of BN/PA12T composites prepared by different methods
图 7 不同方法制备的BN/PA12T复合材料的拉伸(a)和弯曲(b)性能
Figure 7. Tensile (a) and flexural (b) properties of BN/PA12T composites prepared by different methods
图 8 混合溶剂分散法制备的BN/PA12T复合材料在氮气气氛下的TG (a)和DTG (b)曲线
Figure 8. TG (a) and DTG (b) curves of BN/PA12T composites prepared by mixed solvent dispersion method under N2 atmosphere
图 9 混合溶剂分散法制备的BN/PA12T复合材料的维卡软化温度
Figure 9. Vicat softening temperatures of BN/PA12T composites prepared by mixed solvent dispersion method
图 10 混合溶剂分散法制备的BN/PA12T复合材料的介电常数
Figure 10. Dielectric constant of the BN/PA12T composites prepared by mixed solvent dispersion method
表 1 BN的取向度分析
Table 1. Analysis on the orientation degree of BN
BN content/wt% Preparation
methodsI(002) I(100) I(002)/I(100) 10 MSD 63324 2369 27 10 MM 22879 4133 6 20 MSD 93765 3610 26 20 MM 50005 5838 9 30 MSD 89145 6069 15 30 MM 65127 7285 9 40 MSD 106008 7416 14 40 MM 97303 8151 12 Note: I—Intensity. 
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表 2 热塑性耐高温聚合物基导热复合材料的导热率
Table 2. Thermal conductivities of thermoplastic heat-resistance polymer-based composites
Matrix Filler Content TC/
(W·(m·K)−1)Preparation method/
Testing methodYear Liquid crystral polymer (LCP) BN (~60 μm) 33vol% 3.29 Clamped-air-cooling/Heat flow 2013[31] Poly(ether ether ketone)
(PEEK)BN nanopowders (~70 nm) 30wt% 1.04 Casting/LFA 2021[32] Poly(ether ether ketone)
(PEEK)BN (4-10 μm) 30wt% 1.01 Hot pressing/LFA 2020[33] Polyetherimide (PEI) Non-covalent modified BN 30wt% 0.82 Hot pressing/LFA 2021[34] Polyetherimide (PEI) Polyimide-coated BN 60wt% 2.55 Injection molding/LFA 2014[35] Polyphenylene sulfide (PPS) Micrometer BN/nanometer BN 60wt% 2.64 Hot pressing/Hot disk 2017[36] Polyphenylene sulfide (PPS) Siloxane modified BN 50wt% 1.60 Injection molding/LFA 2018[37] Polyphenylene sulfide (PPS) Siloxane modified nanometer BN 60wt% 1.12 Hot pressing/Hot disk 2017[38] Thermoplastic polyimide (TPI) Silver nanowires-decorated multi-walled carbon nanotubes 3wt% 0.44 Casting/Transient hot-wire 2022[39] Polyamide 46 (PA46) Carbon fiber (Diameter=7.2 μm, Aspect ratio=7) 40wt% 1.49 Injection molding/LFA 2017[40] PA12T BN (2-4 μm) 40wt% 2.73 Mixed solvent dispersion/LFA This work Notes: TC—Thermal conductivity; LFA—Laser flash apparatus.
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表 3 混合溶剂分散法制备的BN/PA12T复合材料的热失重性能
Table 3. Thermogravimetic analysis of BN/PA12T composites prepared by mixed solvent dispersion method
BN content/wt% T5%/℃ Tmax/℃ −Vmax/(%·℃−1) ω/% (600℃) 0 439 476 3.018 1.353 10 442 473 2.654 10.375 20 441 474 2.426 21.261 30 444 473 2.146 30.852 40 446 472 1.896 39.622 Notes: T5%—Decomposition temperature in 5wt% mass loss fraction; Tmax—Temperature corresponding to the maximum decomposition rate; −Vmax—Maximum decomposition rate; ω—Mass residual rate at 600℃.
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表 4 混合溶剂分散法制备的BN/PA12T复合材料的介电损耗
Table 4. Dielectric loss of BN/PA12T composites prepared by mixed solvent dispersion method
BN content/wt% Dielectric loss/(106 Hz) 0 0.050 10 0.041 20 0.033 30 0.025 40 0.016
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