Crystallization Behavior of Polymers as Viewed from the Molecular Level

The structural changes viewed from the molecular level have been investigated for the isothermal crystallization phenomena of polyethylene (PE) and the solvent-induced crystallization phenomenon of syndiotactic polystyrene (sPS) glassy sample. The data, which were collected by the time-resolved measurements of Fourier-transform infrared spectra, Raman spectra, synchrotron-sourced small-angle X-ray scattering, wide-angle X-ray scattering, and so on, were combined together to extract the detailed structural information in these phase transition phenomena. In the case of PE, the isothermal crystallization from the melt to the orthorhombic form was found to occur via the conformationally-disordered trans chain form, followed by the formation of the lamellar stacking structure of regular orthorhombic-type crystals. In the case of sPS, the amorphous chains in the glassy sample were found to enhance the mobility through the interaction with the injected solvent molecules, which act as a trigger to cause the conformational ordering from the random coil to the regular T$_2$G$_2$-type helical form. The thus created short helical segments were found to grow into longer helices, which gathered together to form the crystallites, as revealed by the organized coupling of the infrared, Raman and X-ray scattering data.