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Polymer nanofibers with high thermal conductivities and outstanding thermalstabilities are highly desirable in heat transfer-critical applications such asthermal management, heat exchangers and energy storage. In this work, we unlockthe fundamental relations between the thermal conductivity and thermalstability of polymer nanofibers and their molecular characteristics by studyingthe temperature-induced phase transitions and thermal transport of a series ofpolymer nanofibers. Ten different polymer nanofibers with systematically chosenmolecular structures are studied using large scale molecular dynamicssimulations. We found that high thermal conductivity and good thermal stabilitycan be achieved in polymers with rigid backbones, exemplified by{\pi}-conjugated polymers, due to suppressed segmental rotations and largephonon group velocities. The low probability of segmental rotation does notonly prevent temperature-induced phase transition but also enables long phononmean free paths due to reduced disorder scattering. Although strongerinter-chain interactions can also improve the thermal stability, polymers withsuch a feature usually have heavier atoms, weaker backbone bonds, and segmentsvulnerable to random rotations, which lead to low thermal conductivities. Thiswork elucidates the underlying linkage between the molecular nature andmacroscopic thermal properties of polymer nanofibers, which is instrumental tothe design of thermally conductive polymer nanofibers with high temperaturestabilities.

journal of physical chemistry. c./journal of physical chemistry. c

Polymer Nanofibers with Outstanding Thermal Conductivity and Thermal  Stability: Fundamental Linkage between Molecular Characteristics and  Macroscopic Thermal Properties