Crystallization in blend of polycaprolactone and high molecular weight polyethylene oxide

The concentration distribution in blend of polyethylene oxide (PEO)/polycaprolactone (PCL) and subsequent crystallization were investigated with differential scanning calorimetry, in-situ small angle X-ray scattering and wide angle X-ray scattering. By using PEOs with a molecular weight of 1 × 10⁶ g/mol (PEO1M) and 1 × 10⁵ g/mol (PEO100k), respectively, it is revealed that in initial blend the concentration of PEO1M in PEO-rich region is higher than that determined by miscibility. This non-equilibrium distribution induced by crystallization is maintained after melting, since slow relaxation of PEO1M hinders the redistribution process. Crystallization behavior of blend with 25 % of PEO1M at different melting temperatures was further investigated. The crystallinity shows no dependence on melting temperature, while the long period of PEO1M decreases continuously when melting temperature exceeds 140 °C. This decrease indicates more PCL chains diffuse into PEO-rich regions with increasing temperature and molten PCL chains reduce the entanglement number of PEO1M as solvent. Moreover, the periodicity of PEO1M lamellae becomes worse when crystallization proceeds faster, which is related to slower exclusion of PCL chains.