Crystallization of polyethylene under shear flow as studied by time resolved depolarized light scattering. Effects of shear rate and shear strain

We have studied structure formation during crystallization of polyethylene (PE) under shear flow using time resolved depolarized light scattering (DPLS) in order to elucidate the formation mechanism of the so-called shish-kebab structure. Two-dimensional (2D) DPLS pattern clearly showed streak-like scattering normal to the flow direction in the early stage during the crystallization after pulse shear, suggesting the formation of the shish-like structure in μm scale. In order to analyze the 2D DPLS pattern we defined measures for the acceleration of the crystallization rate and the degree of anisotropy and found that there are critical shear rates for both of the acceleration and the anisotropy at a given shear strain: the former is much smaller than the latter. We also determined the critical shear rate for the anisotropy as a function of the shear strain. Extrapolating to inverse of the infinite shear strain=0, we found the critical shear rate for the anisotropy at the infinite shear strain to be 1.5 s−1. The results were discussed in relation to a competition between the relaxation rate of polymer chains and the orientation-induced crystallization rate.