Thermally conductive epoxy resin composites are widely used as electrical equipment insulation and package materials to enhance heat dissipation. It is important to explore the dielectric properties of the composites at high temperatures for the safe operation of the equipment. This paper investigated the charge transport behavior of an epoxy/nano−SiO2/micro−BN composite at varied temperatures by combined analysis of the TSDC (thermally stimulated current), conduction current, complex permittivity and space charge distribution between 40 and 200 °C. The results show that ionic space charge accumulation was significantly suppressed in the composite at high temperatures. The conduction current increased gradually with temperature and manifested a remarkable shift from electron charge transport to ion charge transport near the glass transition temperature (Tg). The real and imaginary permittivity showed an enormous increase above Tg for both the epoxy resin and the composite. The conduction current and permittivity of the composite were remarkably reduced in comparison to the epoxy resin. Therefore, the ionic process dominated the high temperature dielectric properties of the epoxy resin and the composite. The nano–micro fillers in the composite can significantly inhibit ion transport and accumulation, which can significantly enhance the dielectric properties of epoxy resin. Thus, the nano–micro composite has a strong potential application as a package material and insulation material for electronic devices and electrical equipment operated at high temperatures.
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