Refined NMR analysis of the phase structure of solution‐crystallized linear polyethylene

Nuclear magnetic resonance (NMR) spectroscopy reveals that solution‐grown polyethylene samples have a unique phase structure independent of molecular weight. The lamellar crystallites are composed of about 85% crystalline material with the noncrystalline overlayer as large as 15%. The molecular motion in the overlayer is comparatively hindered and the liquid‐like component, which is generally recognized in melt‐grown crystals, cannot be produced appreciably, even at 60°C. Such hindered molecular mobility can be understood in terms of a rather restricted conformation of the molecular chains in the noncrystalline overlayer, arising from the special mode of crystallization from dilute solution.