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Polypropylene/poly(ε-caprolactone) (PP/PCL) blends were prepared by melt mixing. The thermal behaviour of the blends was investigated using differential scanning calorimetry (DSC) and dynamical rheology in the solid state (RSA). Both non-isothermal and isothermal crystallizations were performed. The Avrami equation was applied to the latter case. DSC and RSA results demonstrated in agreement with morphological observations that PP/PCL blends are immiscible in the whole composition range. PP acts as a nucleating agent for PCL, and when PP forms the disperse phase, it crystallizes in a fractionated fashion. When PCL is the disperse phase, it exhibits an unexpected melting point depression after cooling at 10 °C/min. Such depression was not observed after isothermal crystallizations, indicating that under non-isothermal crystallization kinetic problems show up. Thus, global crystallization is governed by a competition between nucleation and diffusion, which depends on crystallization conditions and composition.

Nucleation versus melting point depression of the polycaprolactone phase in polypropylene/polycaprolactone blends