Divining the shape of nascent polymer crystal nuclei

We demonstrate that nascent polymer crystals (i.e., nuclei) are anisotropic entities with neither spherical nor cylindrical geometry, in contrast to previous assumptions. In fact, cylindrical, spherical, and other high symmetry geometries are thermodynamically unfavorable. Moreover, postcritical transitions are necessary to achieve the lamellae that ultimately arise during the crystallization of semicrystalline polymers. We also highlight how inaccurate treatments of polymer nucleation can lead to substantial errors (e.g., orders of magnitude discrepancies in predicted nucleation rates). These insights are based on quantitative analysis of over four million crystal clusters from the crystallization of prototypical entangled polyethylene melts. New comprehensive bottom-up models are needed to capture polymer nucleation.We demonstrate that nascent polymer crystals (i.e., nuclei) are anisotropic entities with neither spherical nor cylindrical geometry, in contrast to previous assumptions. In fact, cylindrical, spherical, and other high symmetry geometries are thermodynamically unfavorable. Moreover, postcritical transitions are necessary to achieve the lamellae that ultimately arise during the crystallization of semicrystalline polymers. We also highlight how inaccurate treatments of polymer nucleation can lead to substantial errors (e.g., orders of magnitude discrepancies in predicted nucleation rates). These insights are based on quantitative analysis of over four million crystal clusters from the crystallization of prototypical entangled polyethylene melts. New comprehensive bottom-up models are needed to capture polymer nucleation.