Enhanced out-of-plane thermal conductivity of polyimide composite films by adding hollow cube-like boron nitride

Boron nitride nanosheet (BNNS) is widely used in electronic thermal management due to its excellent planar thermal conductivity and insulating properties. However, it is challenging to improve the out-of-plane thermal conductivity of BNNS-doped composites due to the anisotropy of the thermal conductivity of BNNS. Therefore, the BNNS in the matrix must be oriented to obtain composites with high out-of-plane thermal conductivity. In this study, BNNS powders with directional structures were synthesized directly using sodium chloride templates. The as-obtained BNNS powders have a unique hollow cube-like structure with an ultra-low density of 2.67 × 10⁻² g/cm³ and nearly 8 times the volume of the same mass of two-dimensional (2D) BNNS, making it easy to form the out-of-plane thermal conductivity paths in the polymer matrix. In addition, the high out-of-plane thermal conductivity of 4.93 W m⁻¹ K⁻¹ at 23.3 wt% loadings was obtained by doping it into a polyimide (PI) matrix. This value is 9.7 times higher than that of 2D BNNS-doped PI at the same loadings, 17.6 times higher than pure PI, and 6.1 times higher than the thermally conductive PI film sold by DuPont. Therefore, the prepared composite film has great potential for application in electronic thermal management.     

氮化硼纳米片改性复合材料导热性能的研究进展

氮化硼纳米片（BNNSs）是一种二维片状纳米材料，具有较高的导热性和热稳定性。将其作为填料加入聚合物中，可显著提高复合材料的导热性能。本文基于近年来对BNNSs改性复合材料的导热性能的研究进展，总结了BNNSs制备和改性的方法以及建立导热路径的方法，介绍了该体系复合材料的导热机理，分析了影响复合材料导热性能的因素，最后对提高复合材料的导热性能进行了展望。     

Electrically insulating polymeric nanocomposites with enhanced thermal conductivity by visible‐light curing of epoxy–boron nitride nanotube formulations

Epoxy–boron nitride nanotube (BNNT) composites were prepared using visible light through a radical‐induced cationic polymerization method activated by camphorquinone. The fully cured films showed an enhancement of glass transition temperature in the presence of the filler. Electrical characterization showed a slight dielectric constant decrease with BNNT content. Finally, thermal conductivity measured using nano‐flash analysis showed a linear increase in the thermal conductivity of the materials with increasing BNNT content in the photocurable formulations. © 2017 Society of Chemical Industry     

Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites

The enhancement of the thermal conductivity, keeping the electrical insulation, of epoxy thermosets through the addition of pristine and oxidized carbon nanotubes (CNTs) and microplatelets of boron nitride (BN) was studied. Two different epoxy resins were selected: a cycloaliphatic (ECC) epoxy resin and a glycidylic (DGEBA) epoxy resin. The characteristics of the composites prepared were evaluated and compared in terms of thermal, thermomechanical, rheological and electrical properties. Two different dispersion methods were used in the addition of pristine and oxidized CNTs depending on the type of epoxy resin used. Slight changes in the kinetics of the curing reaction were observed in the presence of the fillers. The addition of pristine CNTs led to a greater enhancement of the mechanical properties of the ECC composite whereas the oxidized CNTs presented a greater effect in the DGEBA matrix. The addition of CNTs alone led to a marked decrease of the electrical resistivity of the composites. Nevertheless, in the presence of BN, which is an electrically insulating material, it was possible to increase the proportion of pristine CNTs to 0.25 wt% in the formulation without deterioration of the electrical resistivity. A small but significant synergic effect was determined when both fillers were added together. Improvements of about 750% and 400% in thermal conductivity were obtained in comparison to the neat epoxy matrix for the ECC and DGEBA composites, respectively. © 2019 Society of Chemical Industry     

Highly thermally conductive hexagonal boron nitride/alumina composite made from commercial hexagonal boron nitride

Hexagonal BN is an unusual material in that it is both highly thermally conductive as well as an electrical insulator. Additionally, hBN is also thermally stable in air. This unusual combination of properties makes hBN of significant interest for thermal management. Unfortunately, hBN is not easily consolidated into substrates without the addition of second phases which generally result in poorer thermal performance. This research investigates the potential to utilize this material to dissipate heat from high‐voltage, high‐power electrical devices. Specifically, a process to coat individual platelets of commercial hexagonal BN powder with a layer of amorphous aluminum oxide was developed. The coated hexagonal BN was then hot‐pressed to form a highly thermally conductive substrate. The process to coat hexagonal BN platelets with aluminum oxide was accomplished by mixing hexagonal BN with AlCl₃ containing some water, then evaporation of excess AlCl₃ to form a Al, Cl, and O layer on hexagonal BN. This product was then heated in air to convert the surface layer into aluminum oxide. Following hot pressing to 1950°C and 10 ksi, the consolidated composite has through‐plane and in‐plane thermal conductivity of 14 and 157 W·(m·K)^?1, respectively, at room temperature.     

Noncovalent functionalization of boron nitride and its effect on the thermal conductivity of polycarbonate composites

Polycarbonate (PC) is an engineering thermoplastic with excellent insulation and mechanical properties. However, the low thermal conductivity restricted its application in electronic devices. Hexagonal boron nitride (h ‐BN) microparticle, a promising material with high thermal conductivity, was functionalized with cationic polyacrylamide (CPAM) and introduced into PC matrix to improve the thermal conductivity. SEM and XRD analysis showed that the modified BN (CBN) particles oriented and formed thermal conductive pathways within PC matrix. The formation of large‐area oriented CBN significantly improved the thermal conductivity and thermal stability of composites. At 20 wt % CBN loading, the thermal conductivity of 0.7341 Wm^?1 K^?1 and the temperature for 5% weight loss (T ₅) of 498.6 °C were obtained, which was 3.1 times and 77 °C higher than that of pure PC, respectively. Furthermore, outstanding electrical insulation property of matrix was retained in the composites. These results revealed that PC/CBN composite was a promising material for thermal management and electrical enclosure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44978.     

增韧导热环氧树脂/氮化硼复合材料的制备与表征

采用种子乳液聚合方法制备了聚（丙烯酸正丁酯/甲基丙烯酸甲酯-co-甲基丙烯酸缩水甘油酯）核壳增韧剂（PBMG）,并用湿法球磨与超声辅助相结合的方法对六方氮化硼（h-BN）进行改性,制备的改性氮化硼（MBN）可提高环氧树脂（EP）的热导率。最后采用机械共混方法制备了环氧树脂/增韧剂/改性氮化硼（EP/PBMG/MBN）复合材料。通过透射电子显微镜（TEM）、扫描电子显微镜（SEM）、X射线衍射（XRD）、动态激光光散射（DLS）、热导率和力学性能等测试对核壳增韧剂的粒子形成、改性氮化硼和复合材料进行了表征。结果发现：最终制备的聚丙烯酸酯乳胶粒子呈现明显的核壳结构,且粒度分布很窄。当聚丙烯酸酯增韧剂添加量为5%、改性氮化硼为8.99%时,环氧树脂/增韧剂/改性氮化硼复合材料的冲击强度和热导率比纯环氧树脂（EP）的分别提高了133%和171%。随着未来的基板材料要求有效的热耗散,这种复合材料有望用于微电子工业上。     

Alkylated modified boron nitride nanosheets/polyimide composite films with advanced thermal conductivity and low dielectric constant

Owing to the rapid development of the latest micro-electronic devices, polymer composite materials that combine high thermal conductivity and low permittivity have aroused the interest of researchers. However, it is a huge challenge to balance the above parameters. In this work, hexagonal boron nitride (h-BN) powder was ultrasonically exfoliated to obtain alkylated boron nitride nanosheets (Alkyl-BNNS). Then, a series of polyimide (PI) composites were synthesized with different amounts of Alkyl-BNNS. Attributed to more robust interfacial non-covalent interactions between Alkyl-BNNS and polymer chains to inhibit interfacial polarization, Alkyl-BNNS can be scattered well in PI substrate. Thus, the obtained PI composite behaved a high thermal conductivity of 6.21 W/(mK) and a low dielectric constant (3.23) under the load of 20 wt%. Besides, Alkyl-BNNS/PI composites have efficient thermal management capability, low water absorption, favorable electrical resistance, and prominent tensile strength. Importantly, these composite films are expected to be excellent candidates in the field of microelectronics.     

Crystallization and thermal conductivity of poly (vinylidene fluoride)/boron nitride nanosheets composites

ABSTRACT

In this work, boron nitride (BN) and exfoliated boron nitride nanosheets (BNNs) were employed as thermal conductive fillers to improve the thermal conductivity of poly(vinylidene fluoride) (PVDF) composites. Results suggested that the thermal conductivity of PVDF increases significantly with an increase in loading content of functional fillers. When the mass ratio of fillers was more than 30 wt%, the heat conduction network was formed. BNNs were capable of forming denser heat conduction network as per the SEM observations. In this scenario, PVDF/BNNs composites demonstrated excellent thermal conductivity. For example, the thermal conductivity of PVDF/BNNs (60/40) was 0.82 W/mK, which was 2.4 times and 17% higher than that of neat PVDF and PVDF/BN (60/40) counterpart, respectively. The non-isothermal crystallization of corresponding composite was studied by Mo method. Combining with XRD results, both BN and BNNs acted as the nucleation agents but had no effect on crystal forms.     

Effective surface treatments for enhancing the thermal conductivity of BN‐filled epoxy composite

To improve the thermal conductivity of BN‐filled epoxy composite, admicellar polymerization was used to coat polystyrene and polymethyl methacrylate on the BN surface to improve the interfacial adhesion in the composite. The treated surface was characterized by FTIR and contact angle measurements. The results show that the admicellar treatment led to improved wettability of epoxy resin on the treated surface. Thermal conductivity of the composite increased from 1.5 W/mK for untreated BN to 2.69 W/mK when the admicellar‐treated BN was used, indicating improvement in the interfacial adhesion between BN and epoxy resin in the composite. The mechanical properties of the composite also improved significantly. The surfactant : monomer molar ratio of 1 : 10 was found to be the optimum condition for the admicellar polymerization process. The solubility parameter concept was used to explain the difference in the effectiveness of polystyrene and polymethyl methacrylate. When compared to the more conventional silane treatment, admicellar treatment was found to be more effective in improving the interfacial adhesion between the BN particles and epoxy resin. SEM micrographs of the fractured surface of the composite further confirm the improvement in the interfacial adhesion after the admicellar treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microwave‐assisted in situ polymerization of polycaprolactone/boron nitride composites with enhanced thermal conductivity and mechanical properties

Polycaprolactone/boron nitride (PCL/BN) composites were prepared by microwave‐assisted ring‐opening polymerization of ε‐caprolactone (ε‐CL). In order to improve the dispersibility and interfacial interaction between BN fillers and PCL matrix, hydroxyl functional BN (mBN) was first prepared to be used as a macroinitiator for ε‐CL. Then BN grafted PCL (BN‐g‐PCL) copolymers were obtained via the in situ method, which acted as in situ compatibilizers in the PCL/BN composites. Various techniques were applied to characterize the mBN and PCL/BN composites. The Fourier transform infrared spectroscopy results confirm the structure of the BN‐g‐PCL copolymer. Field emission SEM graphs exhibit that, for the PCL/mBN composites, the mBN presents a homogeneous dispersion in the matrix and interfacial adhesion between the PCL and mBN is improved. These are beneficial for enhancing the thermal conductivity of the PCL/mBN composites. Notably, the PCL/mBN composite with 5 wt% mBN loading achieves the highest thermal conductivity of 0.55 W m^?1 K^?1, which is 2.75 times higher than that of pure PCL, 0.20 W m^?1 K^?1. This indicates that the excellent dispersion and interfacial adhesion could lead to the construction of continuous thermal conductive paths at a low BN loading and reduce the heat loss caused by phonon scattering in the interface. Furthermore, mBN could help to improve the mechanical properties of the composite. On adding 5 wt% mBN, the tensile strength and tensile modulus of the composite are 1.58 and 2.05 times higher, respectively, than those of PCL. © 2020 Society of Chemical Industry     

Liquid crystal epoxy composites based on functionalized boron nitride: Synthesis and thermal properties

A composite was prepared by in-situ polymerization of liquid crystal epoxy (LCE₄) with a low dielectric and high thermal conductivity boron nitride (BN) filler, which the filler (f-BN) was surface-functionalized by γ-glycidoxypropyltrimethoxysilane (KH560) and aminopropylisobutyl polyhedral oligomeric silsesquioxane (NH₂-POSS). The surface-functionalized BN was more uniformly dispersed in LCE₄, which improved the interfacial compatibility between inorganic and organic phases. Compared with pure LCE₄, KH560, and NH₂-POSS modified f-BN/LCE₄ composites exhibited a higher glass transition temperature, better thermal stability, and higher thermal conductivity. For example, when the f-BN content reached 30 wt%, the energy storage modulus of the composite increased to 2580 MPa, and the glass transition temperature was 103°C. The thermal conductivity of this 30 wt% f-BN composite was 0.48 W m⁻¹ K⁻¹, 128.6% higher than that of pure LCE₄. In addition, thermal stability, low hygroscopicity, and dielectric properties of the composites were characterized and analyzed to explore the application prospects of f-BN/LCE₄ composites in electronic packaging and in high-performance microelectronic devices.     

Synergistic enhancement of thermal conductivity by addition of graphene nanoplatelets to three-dimensional boron nitride scaffolds for polyamide 6 composites

Three-dimensional boron nitride/graphene nanoplatelets (3D-BN-GNP) scaffolds were fabricated using an ice-templating method and polyamide 6 (PA6)-based composites were prepared by vacuum impregnation of caprolactam monomers into the scaffolds, followed by polymerization. The BN sheets in the PA6/3D-BN and PA6/3D-BN-GNP composites display a predominant parallel alignment along the ice-crystal formation constructing thermally conductive paths. The addition of few GNPs assists the dispersion of BN sheets in the PA6/3D-BN-GNP composites and repair the broken thermal paths caused by local agglomeration of the BN sheets. Consequently, GNPs play a morphology-promoted synergistic role in the enhancement of the thermal conductivity of the PA6/3D-BN-GNP composites. The PA6/3D-BN-GNP composite prepared with 23.40 wt% BN sheets and 2.60 wt% GNPs exhibits the highest thermal conductivity of 2.80 W m⁻¹ K⁻¹, which is 833% and 33% higher than the values recorded for the pure PA6 and the PA6/3D-BN composite at BN loading of 26.18 wt%, respectively. Infrared imaging analysis revealed that the surface of the PA6/3D-BN-GNP composite has a fast response to heating and cooling, suggesting the potential of the composites in thermal management applications.     

六方氮化硼复合氧化铝耐火材料的性能研究

以粒度为3~1和≤1 mm的板状刚玉为骨料,板状刚玉细粉、α-Al2O3微粉和Si粉为细粉,分别添加质量分数为3%的六方氮化硼、3%和10%的鳞片石墨制备了Al2O3-BN和低碳、高碳Al2O3-C三种试样,并对比了其常温物理性能、高温强度、抗氧化性、抗热震性和抗渣侵蚀性。结果表明:1)Al2O3-BN耐火材料的常温、高温物理性能与低碳铝碳材料相差不大,并优于传统高碳铝碳材料;2)Al2O3-BN耐火材料具有比碳复合耐火材料更好的抗热震性和抗氧化性,抗渣性与低碳铝碳材料的相当;3)考虑到材料的整体性能,六方氮化硼可以替代石墨作为原料,用于制备综合性能优异的氧化铝质复合耐火材料。     

Thermal properties of polymer-derived ceramic reinforced with boron nitride nanotubes

We report the thermal properties of boron nitride nanotube (BNNT) reinforced ceramic composites using the polymer derived ceramic (PDC) processing route. The nano-composites had a BNNT loading of up to 35.4 vol.%. TGA results showed that nano-composites have good thermal stability up to 900°C in air. BNNTs in nano-composites survived in an oxidizing environment up to 900°C, revealing that nano-composites can be used for high temperature applications. Thermal conductivity of PDC reinforced with 35.4 vol.% BNNT was measured as 4.123 W/(m·K) at room temperature, which is a 2100 % increase compared to that of pristine PDC. The thermal conductivity value increases with the increase of BNNT content. A thermal conductivity percolation phenomenon appeared when the BNNT content increased to 36 ± 5 vol.%. The results of this study showed that BNNTs could effectively improve the thermal conductivity of PDC materials. BNNT reinforced PDC could be used as thermal structural materials in a harsh environment at temperatures up to 900°C.     

Enhanced dielectric permittivity and thermal conductivity of hexagonal boron nitride/poly(arylene ether nitrile) composites through magnetic alignment and mussel inspired co-modification

In this work, we present novel hexagonal boron nitride (h-BN)/poly(arylene ether nitrile) nanocomposites with high dielectric permittivity and thermal conductivity. For this purpose, the interfacial adhesion and orientation of nanofillers are the two key factors that need to be considered. Firstly, iron oxide was attached onto the surface of h-BN to obtain magnetically responsive property, which would realize the orientation of h-BN by applying an external magnetic field during the preparation process of PEN composites. Secondly, the magnetic h-BN was further modified by mussel-inspired method with dopamine and secondary functional monomer (KH550). It was found that the alignment of h-BN and improvement of interfacial adhesion resulted in the interesting properties of PEN composites. With addition of 30 wt% modified h-BN, the dielectric permittivity of PEN composites was increased from 3.2 of neat PEN to 16.4 (increased by 413%), and the low dielectric loss was remained. Meanwhile, the thermal conductivity was enhanced to 0.662 W/m K (increased by 140%) at the same loading content. In addition, the resulting h-BN/PEN nanocomposites maintained high mechanical strength and thermal stability even the nanofillers loading content reached 30 wt%. Therefore, the dielectric and thermally conductive h-BN/PEN composites with high mechanical strength and thermal stability have big advantages in the area of energy storage devices.     

Anchoring carbon nanotubes to boron nitride microrods for enhancing the thermal conductivity of polystyrene

The development of high-performance thermally conductive fillers is crucial for the thermal management of polymer-based composites. Herein, a facile precursor pyrolysis strategy was adopted to fabricate boron nitride@multiwalled carbon nanotubes (BN@MWCNTs) fillers, wherein uniformly distributed MWCNTs were firmly anchored on BN microrods. Benefiting from the unique structure, the BN@MWCNTs act as fillers in the design of polystyrene (PS)/BN@MWCNTs composites via in situ polymerization. As a result, a 7.74-fold higher thermal conductivity (TC) (9.55 W/m·K) was achieved for the 10 wt% BN@MWCNTs, as compared to native PS/BN/MWCNTs prepared by the conventional melt-mixing method. More importantly, the PS/BN@MWCNTs composites exhibited satisfactory electrical insulation owing to the isolation effect of BN. Overall, this work provides a promising frontier for the design of polymer-based thermally conducting materials for applications in thermal management.     

The effect of boron nitride nanosheets on the mechanical and thermal properties of aluminum nitride ceramics

The boron nitride nanosheets (BNNSs)/aluminum nitride (AlN) composites were prepared by hot press sintering at 1600°C. The microstructure, mechanical properties, and thermal conductivity of the samples were measured, and the effect of adding BNNSs to AlN ceramics on the properties was studied. It is found that the addition of BNNSs can effectively improve the mechanical properties of AlN. When the additional amount is 1 wt%, the bending strength of the sample reaches the maximum value of 456.6 MPa, which is 23.1% higher than that of the AlN sample without BNNSs. The fracture toughness of the sample is 4.47 MPa m^1/2, a 68.7% improvement over the sample without BNNSs. The composites obtained in the experiment have brilliant mechanical properties.     

镍铁–立方氮化硼复合电刷镀工艺研究

通过复合电刷镀在20钢基体表面制备镍铁–立方氮化硼(CBN)复合镀层。研究了施镀电压、镀液温度及镀笔速率对复合镀层中CBN含量的影响,分析了镀层中CBN含量与耐磨性之间的关系。复合电刷镀NiFe–CBN的镀液组成和最佳工艺条件为:NiSO4·6H2O 270~300 g/L,FeCl2·2H2O 23~27 g/L,H3BO326~30 g/L,Na3C6H5O7·2H2O 20~30 g/L,糖精2~3 g/L,十六烷基三甲基溴化铵0.2~0.3 g/L,pH 3.2~4.0,电压14 V,温度50°C,镀笔速率15 m/min,时间100~120 min。在最佳工艺下所得镀层的CBN质量分数为9.8%,显微硬度为770 HV,耐磨性和结合力良好。