Cross Nucleation in Polyethylene with Precisely Spaced Ethyl Branches.

In cross nucleation, an early nucleating crystalline polymorph (A) nucleates another crystalline polymorph (B) of higher or lower thermodynamic stability without undergoing a polymorphic transformation. Although this phenomenon was recently observed in the crystallization process of several small molecules, there has been insufficient evidence for cross nucleation in a crystalline polymer. In this paper, we report cross nucleation behavior during an isothermal crystallization of a crystalline polymer with precisely spaced branches. Polyethylene with ethyl branches on every 21st carbon exhibited growth of new spherulites at the growth front of an initially formed spherulite. The radial growth rate of the initially formed spherulite and the newly grown spherulite calculated from polarized optical microscope data were 0.76 μm/min and 1.01 μm/min, respectively. The growth rate of the newly grown spherulite is faster than that of the initially formed spherulite, which meets a required condition for cross nucleation. Scanning microbeam wide-angle X-ray scattering (WAXS) confirmed that the crystalline polymorphs of the two kinds of spherulites are not the same.