Thermally Conductive and Electrically Insulating Epoxy Composites Filled with Network-like Alumina In Situ Coated Graphene.

With the rapid development of the electronics industry, there is a growing demand for packaging materials that possess both high thermal conductivity (TC) and low electrical conductivity (EC). However, traditional insulating fillers such as boron nitride, aluminum nitride, and alumina (Al2O3) have relatively low intrinsic TC. When graphene, which exhibits both superhigh TC and EC, is used as a filler to fill epoxy resin, the TC of blends can be much higher than that of blends containing more traditional fillers. However, the high EC of graphene limits its application in cases where electrical insulation is required. To address this challenge, a method for coating graphene sheets with an in situ grown Al2O3 layer has been proposed for the fabrication of epoxy-based composites with both high TC and low EC. In the presence of a cationic surfactant, a dense Al2O3 layer with a network structure can be formed on the surface of graphene sheets. When the total content of Al2O3 and graphene mixed filler reached 30 wt%, the TC of the epoxy composite reached 0.97 W m-1 K-1, while the EC remained above 1011 Ω·cm. Finite element simulations accurately predicted TC and EC values in accordance with experimental results. This material, with its combination of high TC and good insulation properties, exhibits excellent potential for microelectronic packaging applications.

Vertical Alignment of Anisotropic Fillers Assisted by Expansion Flow in Polymer Composites.

Orientation control of anisotropic one-dimensional (1D) and two-dimensional (2D) materials in solutions is of great importance in many fields ranging from structural materials design, the thermal management, to energy storage. Achieving fine control of vertical alignment of anisotropic fillers (such as graphene, boron nitride (BN), and carbon fiber) remains challenging. This work presents a universal and scalable method for constructing vertically aligned structures of anisotropic fillers in composites assisted by the expansion flow (using 2D BN platelets as a proof-of-concept). BN platelets in the silicone gel strip are oriented in a curved shape that includes vertical alignment in the central area and horizontal alignment close to strip surfaces. Due to the vertical orientation of BN in the central area of strips, a through-plane thermal conductivity as high as 5.65 W m-1 K-1 was obtained, which can be further improved to 6.54 W m-1 K-1 by combining BN and pitch-based carbon fibers. The expansion-flow-assisted alignment can be extended to the manufacture of a variety of polymer composites filled with 1D and 2D materials, which can find wide applications in batteries, electronics, and energy storage devices.

Highly Anisotropic Thermal Conductivity of Three-Dimensional Printed Boron Nitride-Filled Thermoplastic Polyurethane Composites: Effects of Size, Orientation, Viscosity, and Voids.

Extrusion-based three-dimensional (3D) printing techniques usually exhibit anisotropic thermal, mechanical, and electric properties due to the shearing-induced alignment during extrusion. However, the transformation from the extrusion to stacking process is always neglected and its influence on the final properties remains ambiguous. In this work, we adopt two different sized boron nitride (BN) sheets, namely, small-sized BN (S-BN) and large-sized BN (L-BN), to explore their impact on the orientation degree, morphology, and final anisotropic thermal conductivity (TC) of thermoplastic polyurethane (TPU) composites by fused deposition modeling. The transformation from one-dimensional axial alignment in the extruded filament to two-dimensional alignment (horizontal and vertical alignment) in the stacking filament of BN sheets is observed, and its impact on anisotropic TC in three directions is clarified. It is found that L-BN/TPU composites show a high TC of 6.45 W m-1 K-1 at 60 wt % BN content along the printing direction, while at a lower content (<40 wt %), S-BN/TPU composites exhibit a higher TC than L-BN/TPU composites. Effects of orientation, viscosity, and voids are comprehensively considered to elucidate such differences. Finally, heat dissipation tests demonstrate the great potential of 3D printed BN/TPU composites to be used in thermal management applications.

Graphite films/carbon fiber fabric/ polyurethane composites with ultrahigh in-plane thermal conductivity and enhanced mechanical properties.

Thermally conductive composites have attracted great attention in virtue of their crucial role in thermal management. In this work, laminated composites were prepared by laying graphite films (GF) and carbon fiber fabrics (CF) in a certain order, then penetrating thermoplastic polyurethane (TPU), finally hot-pressing. In order to enhance the inter-layer strength, the graphite films were perforated with arrays of 1 mm holes in diameter which have intervals of 4 mm and permit the seeping of liquid TPU through them. The in-plane thermal conductivity (TC) of composite reaches 242 W m-1 K-1 with the loading of 25 vol% GF and 60 vol% CF, which is 1210 times that of pure TPU. The great improvement of TC is ascribed to the thermal conductive pathways formed by continuous GF with ultrahigh TC. The addition of CF enhances markedly the mechanical properties of composites. Bending strength and modulus of composites are 5.56 and 17.09 times that of pure TPU, respectively. The proposed design and manufacture method are facile and effective to obtain polymeric composites simultaneously with high TC and good mechanical properties.

Introduction of stereocomplex crystallites of PLA for the solid and microcellular poly(lactide)/poly(butylene adipate-co-terephthalate) blends.

Solid and microcellular poly(l-lactide)/poly(butylene adipate-co-terephthalate) (PLLA/PBAT) blends with or without poly(d-lactide) (PDLA) were prepared via melt blending and batch foaming process with supercritical carbon dioxide, respectively. The introduction of PDLA on the rheological properties, crystallization behavior and dynamic mechanical properties of the PLLA matrix were investigated. The formed PLA stereocomplex between PLLA and PDLA enhanced the storage modulus and complex viscosity of PLLA/PBAT blends efficiently. Interestingly, the addition of 5 wt% or 10 wt% PDLA in the PLLA/PBAT blends was unfavorable for the PLLA crystallization behavior. The potential reason can be sc-PLA crystallites acting as the physical crosslinking points, which constrained the molecular mobility of the PLLA matrix and even blocked the nucleating effect of PBAT domains. Both the enhanced melt strength and decreased crystallinity of the PLLA matrix are favorable for the cell nucleation and growth and the gas adsorption, respectively. The designed partially foaming of PLLA/PBAT with or without PDLA was carried out to investigate the foaming mechanism. The final cell morphology of PLLA/PBAT foams exhibited typical open-cell structure mainly attributed to the soft immiscible PBAT phase as separated domains. With further addition of PDLA in the PLLA/PBAT blends, the microcellular morphology exhibited decreased average cell size and increased cell density. The sc-PLA crystallites networks in the PLLA matrix acted as cell nucleating agents, which meanwhile resisted the force of cell growth and then prevented the cell collapse.