Rheological rationalization of in situ nanofibrillar structure development: Tailoring of nanohybrid shish-kebab superstructures of poly (lactic acid) crystalline phase

Abstract

The key rheological parameters for in situ development of poly (butylene terephthalate) nanofibrils (PBT NFs) in poly (lactic acid) (PLA) matrix using a tuned melt spinning process were studied. Observation of ellipsoidal PBT domains oriented along a short die was attributed to a low interfacial tension between the blend constituents and fulfilled melt rheological criteria for fibrillation in a simple shear flow. The stability of the deformed droplets under the shear and elongational flows was studied by comparing the droplet breakup time and residence time in each flow field. It was demonstrated that the deformed droplets (ellipses) with an increased robust interface underwent coalescence through pinch-off in the subsequent elongational flow field, and transformed to the nanofibrils with an average diameter comparable to the gyration radius (Rg) of PLA chains. In the fabricated isotropic in situ nanofibrillar composites (NFCs), a random orientation of 2D nanohybrid shish-kebab (NHSK) superstructure was observed as a result of the orthogonal pattern of melt crystallized PLA nanodomains on the PBT NFs surface. The NHSK superstructure established in quiescent bulk through mechanism of geometric confinement (soft epitaxy) enabled us to tailor the crystalline morphology via annealing temperature. In a constant nanofibril content, increasing the isothermal temperature (Tiso) up to 114 °C led to an increase in the kebabs length and interlocking of the adjacent superstructures. A transition to spherulitic crystal morphology was observed due to further temperature increase (Tiso≥117 °C). The observed transition indicated that at higher Tiso, the fewer raw nuclei, which were initiated by soft epitaxy mechanism of PLA chain segments on the PBT NFs at the early stage of nucleation, could conduct self-nucleation and 3D lateral growth. The Avrami model was found to be applicable for interpreting variations of crystallite morphology, crystallization rate, and nucleation mechanisms with PBT NF content and isotherm temperature.