The interphase area appears to have a great impact on nanocomposite (NC) dielectric properties. However, the underlying mechanisms are still poorly understood, mainly because the interphase properties remain unknown. This is even more true if the temperature increases. In this study, a multiscale characterization of polyimide/silicon nitride (PI/Si3N4) NC dielectric properties is performed at various temperatures. Using a nanomechanical characterization approach, the interphase width was

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... ed to be 30 ± 2 nm and 42 ± 3 nm for untreated and silane-treated nanoparticles, respectively. At room temperature, the interphase dielectric permittivity is lower than that of the matrix. It increases with the temperature, and at 150 °C, the interphase and matrix permittivities reach the same value. At the macroscale, an improvement of the dielectric breakdown is observed at high temperature (by a factor of 2 at 300 °C) for NC compared to neat PI. The comparison between nano- and macro-scale measurements leads to the understanding of a strong correlation between interphase properties and NC ones. Indeed, the NC macroscopic dielectric permittivity is well reproduced from nanoscale permittivity results using mixing laws. Finally, a strong correlation between the interphase dielectric permittivity and NC breakdown strength is observed.