The competition between crystallization and demixing in polymer blends. V. Numerical modeling and quantitative evaluation of crystallization-induced composition inhomogeneities

It is well known that crystallization of one component in a polymer blend causes composition profiles around the growing spherulites. Amplitude and width of these profiles, respectively, depend on the ratio between the rates of diffusion and of spherulite growth. They can be determined by suitable experimental means. In the present article, the profiles are modeled, starting from Frank's solution of the diffusion equation in spherical coordinates under the boundary condition of moving walls that simultaneously are sources of the diffusing material. Modeled and experimentally determined profiles in PVDF/PEA and PCL/PS blends agree well. The analysis yields estimates for the diffusion coefficient D in polymeric melts as D ≅ (50 ··· 500) μm²/h. Finally, the interference of the composition profiles around several adjacent spherulites can be demonstrated. © 1996 John Wiley & Sons, Inc.