In Situ Following Oriented Crystallization of Pre-Stretched Poly(ethylene 2,5-Furandicarboxylate) Under Post Heating

Post-processing plays a vital role in the determination of the final structures and properties of oriented materials. As a sustainable candidate of oil-based poly(ethylene terephthalate), biobased poly(ethylene 2,5-furandicarboxylate) (PEF) reflects great promise in green fiber, film, and packaging applications, but it undergoes poor stress-induced crystallization (SIC) under tensile deformation, necessitating a post-processing technique to improve its crystallinity and stability. Here, the structural evolution of pre-stretched PEF under post heating after uniaxial deformation was monitored by online synchrotron X-ray diffraction/scattering, differential scanning calorimetry, and ex situ infrared spectroscopy. The results delineate the significantly enhanced crystallization of pre-deformed PEF that happened far below its cold crystallization temperature. Through the isochronous analyses of the temperature-dependent evolution of mechanical response, the mesophase, crystal structure, orientation factor, chain conformation, and interchain ═C-H···O═C hydrogen bonding, the molecular mechanisms of microstructural transition and oriented crystallization of pre-drawn PEF under post heating were clarified. This research can enhance the understanding of PEF crystallization in an oriented state and provide guidelines on the structural design and technical control for processing high-performance PEF-based materials.