Hexagonal boron nitride (h-BN) composites with the oriented cross-linked liquid crystalline (LC) polyimide have been developed as high thermally conductive materials. Well-dispersed h-BN composite films were obtained, as observed by scanning electron microscopy. The morphology of the composite films was further investigated in detail by the wide-angle X-ray diffraction. The obtained composite films based on the cross-linked LC polyimide showed that the polymer chains vertically aligned in the direction parallel to the films, while those based on the amorphous polyimide showed an isotropic nature. Moreover, the alignment of the cross-linked LC polyimides was maintained, even after increasing the volume fraction of h-BN. This alignment plays an important role in the effective phonon conduction between h-BN and the matrices. Indeed, the thermal diffusivity in the thickness direction of the composite films based on the LC polyimide measured by a temperature wave analysis method was increased to 0.679 mm(2) s(-1) at a 30 vol % h-BN loading, which was higher than that based on the amorphous polyimide.
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