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Development of polymer-based composites with simultaneously high thermal conductivity and breakdown strength has attracted considerable attention owing to their important applications in both electronic and electric industries. In this work, boron nitride (BN) nanofibers (BNNF) are successfully prepared as fillers, which are used for epoxy composites. In addition, the BNNF in epoxy composites are aligned by using a film casting method. The composites show enhanced thermal conductivity and dielectric breakdown strength. For instance, after doping with BNNF of 2 wt%, the thermal conductivity of composites increased by 36.4% in comparison with that of the epoxy matrix. Meanwhile, the breakdown strength of the composite with 1 wt% BNNF is 122.9 kV/mm, which increased by 6.8% more than that of neat epoxy (115.1 kV/mm). Moreover, the composites have maintained a low dielectric constant and alternating current conductivity among the range of full frequency, and show a higher thermal decomposition temperature and glass-transition temperature. The composites with aligning BNNF have wide application prospects in electronic packaging material and printed circuit boards.

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