Extensional Stress-Induced Ductility of Poly(l-lactide) Films: Role of the Entangled Network in Amorphous Regions.

The relationship between the density of the entangled amorphous network and the ductility of oriented poly(l-lactide) (PLLA) films is explored based on the preferential hydrolysis of the amorphous regions in phosphate buffer solution (PBS). PLLA films with a balance of ductility and stiffness have been prepared by the "casting-annealing stretching" based on mechanical rejuvenation, and the structural evolution and mechanical properties at different hydrolysis durations have been identified. Various stages are found during the transition of ductility to brittleness for hydrolyzed PLLA films. First, the elongation at break for hydrolyzed PLLA films remains unchanged in the first stage of hydrolysis and then gradually decreases. Eventually, the films turn to be brittle in the third stage. The strain-hardening modulus (GR) of the hydrolyzed films is utilized to reflect the density of the entangled amorphous network, and a gradual decrease of GR with hydrolysis time indicates the decisive role of the amorphous entanglement network in the mechanical rejuvenation-induced ductility of PLLA. The quantitative relationship between the entangled amorphous network and the stress-induced ductility of PLLA films is revealed. The dependence of deformation behavior on entangled amorphous network density is closely correlated to activated primary structure during deformation. The intact chain network plays a crucial role in sufficiently activating the primary structure to yield and disentanglement during the subsequent necking. These findings could advance the understanding of the PLLA's ductility induced by mechanical rejuvenation and offer guidance for awakening the intrinsic toughness of PLLA.

Reorganization of Hydrogen Bonding in Biobased Polyamide 5,13 under the Thermo-Mechanical Field: Hierarchical Microstructure Evolution and Achieving Excellent Mechanical Performance.

The hierarchical microstructure evolution of an emerging biobased odd-odd polyamide 5,13 (PA5,13) films under the thermo-mechanical field, stepping from hydrogen bond (H-bond) arrangement to the crystalline morphology, has been investigated systematically. It is found that the reorganization of H-bonds under the thermo-mechanical field plays a crucial role in the crystallization of PA5,13. Especially, it is revealed that the crystallization process under the thermo-mechanical field develops along the chain axis direction, while lamellar fragmentation occurs perpendicular to the chain axis. Consequently, a stable and well-organized H-bond arrangement and lengthened lamellae with significant orientation have been constructed. Laudably, an impressive tensile strength of about 500 MPa and modulus of about 4.7 GPa are thus achieved. The present study could provide important guidance for the industrial-scale manufacture of high-performance biobased odd-odd PAs with long polymethylene segment in the dicarboxylic unit combined with a large difference between the polymethylene segments in the dicarboxylic and diamine units.

Regenerated cellulose as template for in-situ synthesis of monoclinic titanium dioxide nanocomposite carbon aerogel towards multiple application in water treatment.

Immobilizing catalyst system faces the challenge of balancing catalysts stability and exposure of active site in water treatment. In this study, a novel in-situ synthesis of monoclinic phase of titanium dioxide (TiO2(B)) in cellulose-derived carbon aerogel (TCA) is proposed for processing multi-task in water treatment. The homogeneous gelation reaction supported the high dispersion of TiO2(B) in carbon skeleton. Meanwhile, TiO2 acts as crosslinker to reinforce cellulose network, then the grain refinement of amorphous TiO2 is limited to obtain TiO2(B) during carbonization. Benefiting from the reinforced structure, TCA remains the porous structure after carbonization and exposes more adsorption site than carbon aerogel blended with anatase particles (ACA). The adsorption performance of TCA are 837.3 mg/g, 1156.2 mg/g and 512.6 mg/g on methylene blue, malachite green and crystal violet, respectively. Compared with ACA, the superior interaction between TiO2 and graphite-like carbon improves the degradation rate of tetracycline from 1.3 × 10-3 min-1 to 8.6 × 10-3 min-1, and maintains the degradation efficiency in 3 rounds cyclic test. Besides, TCA also exhibits nearly twice to ACA on absorption capacity of different oil. This facile in-situ synthesis method offers a new insight in fabricating carbon aerogel immobilized photocatalysts system for multi-task in water treatment.

Durably Ductile, Transparent Polystyrene Based on Extensional Stress-Induced Rejuvenation Stabilized by Styrene-Butadiene Block Copolymer Nanofibrils.

The glassy polymer of polystyrene (PS) enjoys a good reputation as a promising optical material; however, the inherent brittleness hinders its further applications. Conventional toughening methods are realized based on the premise of a sacrifice in transparency and stiffness. In this work, we found an unprecedented strategy to address these obstacles by combining extensional stress-induced ductility and suppressing physical aging. PS-based film with a high stiffness, long-term ductility, and excellent transparency is achieved by introducing a styrene-butadiene block copolymer into the PS matrix and subsequently annealing stretched. A nanofibrillar structure of the polybutadiene (PB) phase is formulated surrounded by a PS matrix, and thus, the elongation at break enhances from 3.1% up to 86.8%, accompanying the yield strength enhanced from 25.5 to 62.2 MPa. More significantly, compared with neat PS, these films survive from physical aging and persistent ductility over time. The morphology deformation induced by stress makes an obvious contribution to the improvement of transparency. Investigating the dynamics of chain segments indicates that the incorporation of the copolymer can restrict rearrangement and local relaxation to the PS chain. This work could pave a potential route toward high-performance PS and might be transferable to other glassy polymers with a fragile character.