In the development of hexagonal boron nitride (h-BN)-based polymeric composites with high thermal conductivity, it is always challenging to achieve a dense filling of h-BN fillers to form a desired high-density thermal transfer network. Here, a series of boron nitride nanosheets (BNNSs)/epoxy resin (EP) bulk composites filled with ultrahigh BNNSs content (65-95 wt %) is successfully constructed through a well-designed mechanical-balling prereaction combined with a general pressure molding method. By means of this method, the highly filled BNNSs fillers are uniformly dispersed and strongly bonded with EP within the composites. As a result, the densely BNNSs-filled composites can exhibit multiple performances. They have excellent mechanical properties, and their maximum compression strength is 30-97 MPa. For a BNNSs/EP composite with filling ultrahigh BNNSs fraction up to 90 wt %, its highly in-plane thermal conductivities (TC) are 6.7 ± 0.1 W m-1 K-1 (at 25 °C) to 8.7 ± 0.2 W m-1 K-1 (200 °C), respectively. In addition, the minimum coefficient of thermal expansion of BNNSs/EP composites is 4.5 ± 1.3 ppm/°C (only ∼4% of that of the neat EP), while their dielectric constants are basically located between 3-4 along with their dielectric loss tangent values exceptionally <0.3 in the ultrahigh frequency range of 12-40 GHz. Additionally, these BNNSs/EP composites exhibit remarkable cycle stability in heat transfer during heating and cooling processes because of their structural robustness. Thus, this type of densely BNNSs-filled BNNSs/EP composite would have great potential for further practical thermal management fields.
Keywords: boron nitride nanosheets; coefficient of thermal expansion; densely BNNSs-filled composites; dielectric behavior at ultrahigh frequency; mechanical properties; thermal conductivity.