The mechanism of thermal conductivity in amorphous polymers, especially polymer fibers, is unclear in comparison with that in inorganic materials. Here, we report the observation of across over of heat conduction behavior from three dimensions (3D) to quasi-one dimension (1D) in Polyimide(PI) nanofibers at a given temperature. A theoretical model based on the random walk theory has been proposed to quantitatively describe the interplay between the inter-chain hopping and the intra-chain hopping in nanofibers. This model explains well the diameter dependence of thermal conductivity and also speculates the upper limit of thermal conductivity of amorphous polymers in the quasi-1D limit.
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