Nucleation of Poly(lactide) Partially Wet Droplets in Ternary Blends with Poly(butylene succinate) and Poly(ε-caprolactone).

This work presents the first investigation on the crystallization behavior of partially wet droplets in immiscible ternary blends. Poly(lactide), poly(ε-caprolactone), and poly(butylene succinate) (PLA, PCL, and PBS, respectively) were melt blended in a 10/45/45 weight ratio to produce a "partial wetting" morphology with droplets of the PLA minor phase located at the interface between the other two major components. The crystallization process of the higher melting PLA droplets was studied by polarized light optical microscopy, while the other components remain in the molten state. We found that neighboring partially wet droplets nucleate in close sequence. This is unexpected since partially wet droplets display points of three-phase contact and, hence, should not touch each other. Moreover, the onset of poly(lactide) crystallization is frequently observed at the interface with molten PCL or PBS, with a significant preference for the former polymer. The observed sequential droplet-to-droplet crystallization is attributed to the weak partial wetting behavior of the PCL/PLA/PBS ternary system. In fact, the contact between the interfacially confined droplets during crystallization due to their mobility can lead to a transition from a partial to a completely wet state, with the formation of thin continuous layers bridging larger partially wet droplets. This allows crystallization to spread sequentially between neighboring domains. Using a simple heterogeneous nucleation model, it is shown that the nucleation of PLA on either PCL or PBS melts is energetically feasible. This study establishes a clear relationship between the unique partial wetting morphology of ternary blends and the nucleation of the minor component, paving the way to the understanding and control of crystallization in multiphasic polymer blends for advanced applications.