Robust, Fully Biodegradable Films of Polyesters Realized by In Situ Formation of an Interconnected Multi-Nanolayer Structure under Extensional Flow

Multilayer structures are not only applied to manipulate properties of synthetic polymer materials such as rainbow films and barrier films but also widely discovered in natural materials like nacre. In this work, in situ formation of an interconnected multi-nanolayer (IMN) structure in poly(butylene adipate-co-terephthalate) (PBAT)/poly(butylene succinate) (PBS) cocontinuous blends is designed by an extensional flow field during a "casting-thermal stretching" process, combining the properties of two components to a large extent. Hierarchical structures including phase morphology, crystal structure, and lamellar crystals in IMN films have been revealed, which clearly identifies the crucial role of extensional flow. The oriented PBAT phase in the IMN structure can be beneficial to the epitaxial growth of PBS crystals onto the PBAT nanolayers, thus improving interfacial adhesions. Furthermore, intense extensional stress can also promote crystallinity and thicken the lamellar structure. Given such distinct features in the fully biodegradable films, a simultaneous enhancement in tear strength, tensile strength, and puncture resistance has been achieved. To the best of our knowledge, the tear strength of IMN films about 285.9 kN/m is the highest level in the previous works of this system. Moreover, the proposed fabrication way of the IMN structure is facile and scalable, which is highly expected to be an efficient strategy for development of structured biodegradable polymers with excellent comprehensive properties.