Anisotropic Thermal Diffusivity of Hexagonal Boron Nitride-Filled Polyimide Films: Effects of Filler Particle Size, Aggregation, Orientation, and Polymer Chain Rigidity

A series of inorganic/organic composite films exhibiting high thermal stability and high thermal diffusivity was prepared from five different grades of flake-shaped hexagonal boron nitride (hBN) and aromatic polyimides (PIs). Thermal diffusivities along the out-of-plane (D-perpendicular to) and in-plane (D-parallel to) directions of hBN/PI films were separately measured and analyzed in terms of particle size, shape, concentration, and orientation, as well as molecular structures of rigid and flexible PI matrices. hBN/PI films filled with large flake-shaped particles exhibited a large anisotropy in D-perpendicular to and D-parallel to due to the strong in-plane orientation of heat-conducting basal plane of hBN, while smaller anisotropy was observed in composites with small flakes and aggregates which tend to orient less in the in plane direction during film processing. The anisotropic thermal diffusion property observed in hBN/PI films exhibited strong correlation with the orientation of hBN particles estimated using scanning electron micrographs (SEM) and wide-angle X-ray diffraction. Moreover, composites of hBN with a rigid-rod PI matrix exhibited much larger anisotropy in D-perpendicular to and D-parallel to than flexible PI-composites, reflecting the effect of the rigid and densely packed PI chains preferentially orienting parallel to the film plane. The thermal conductivities of the hBN/rigid-rod PI films were estimated as 5.4 and 17.5 W/m.K along the out-of-plane and in-plane directions, respectively, which is one of the largest values ever reported.