Interplay between Crystallization and Entanglements in the Amorphous Phase of the Crystal-Fixed Polymer Poly(ϵ-caprolactone)

This work focuses on the influence of amorphous-phase entanglements on the semicrystalline morphology of poly(ϵ-caprolactone). This polyester is classified as crystal-fixed; i.e., it displays no translational chain dynamics in the crystals. We study a wide range of well-entangled samples with molecular weights up to several million using polarization microscopy to assess the lamellar growth rate, small-angle X-ray scattering and proton time-domain NMR to characterize the morphology, and proton multiple-quantum NMR, auxiliary carbon-13 NMR, rheology, and tensile deformation to assess the entangled chain dynamics in the melt and semicrystalline states. We demonstrate a significant increase in the density of entanglements in the amorphous phase relative to the melt. The dependencies of our observables on crystallization temperature and molecular weight suggest that entanglements control the thickness of the amorphous layers. This is rationalized by an only slowly relaxing exclusion zone with enhanced entangl...