Poly(lactic acid) (PLA) exhibits excellent shape memory properties but suffers from brittleness and a high glass transition temperature (T_g), limiting its utility in flexible and durable applications. This study explored the modification of PLA properties through the incorporation of poly(ethylene glycol) (PEG), varying in both content (5–20 wt%) and molecular weight (4000–12,000 g/mol), to enhance its suitability for specific applications, such as medical splints. The PLA/PEG blend, containing 15 wt% PEG and with a molecular weight of 12,000 g/mol, exhibited superior shape fixity (99.27%) and recovery (95.77%) in shape memory tests conducted at a programming temperature (T_p) of 45 °C and a recovery temperature (T_r) of 60 °C. Differential scanning calorimetry (DSC) analysis provided insights into the thermal mechanisms driving shape memory behavior of the PLA/PEG blend. The addition of PEG to the PLA blend resulted in a reduction in T_g and an increase in crystallinity, thereby facilitating enhanced chain mobility and structural reorganization. These thermal changes enhanced the shape fixity and recovery of the PLA/PEG blend. Synchrotron wide-angle X-ray scattering (WAXS) was further employed to elucidate the microstructural evolution of PLA/PEG blends during the shape memory process. Upon stretching, the PLA/PEG chains aligned predominantly along the tensile direction, reflecting strain-induced orientation. During recovery, the PLA/PEG chains underwent isotropic relaxation, reorganizing into their original configurations. This structural reorganization highlighted the critical role of chain mobility and alignment in driving the shape memory behavior of PLA/PEG blends, enabling them to effectively return to their initial shape. Mechanical testing confirmed that increasing PEG content and molecular weight enhanced elongation at break and impact strength, balancing flexibility and strength. These findings demonstrated that PLA/PEG blends, especially with 15 wt% PEG at 12,000 g/mol, offer an optimal combination of shape memory performance and mechanical properties, positioning them as promising candidates for customizable and biodegradable medical applications.

This study illustrated the potential applications of thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) grafted nylon membranes with different grafting yields and grafting architecture. The thermoresponsive gating performance at temperatures below and above the lower critical solution temperature (LCST) of PNIPAm (32 °C) were demonstrated. The linear PNIPAm-grafted nylon membrane exhibited a sharp response over the temperature range 20–40 °C. The grafting yield of 25.5% and 21.9%, for linear and crosslinked PNIPAm respectively, exhibited highest thermoresponsive gating function for water flux and had a stable and repeatable “open-closed” switching function over 5 cycle operations. An excellent oil/water separation was obtained at T < 32 °C, at which the hydrophilic behavior was observed. The linear PNIPAm-grafted nylon membrane with 35% grafting yield had the highest separation efficiency of 99.7%, while PNIPAm structures were found to be independent of the separation efficiency. In addition, the membranes with thermoresponsive gas permeability were successfully achieved. The O₂ and CO₂ transmission rates through the PNIPAm-grafted nylon membranes decreased when the grafting yield increased, showing the better gas barrier property. The permeability ratio of CO₂ to O₂ transmission rates of both PNIPAm architectures at 25 °C and 35 °C were around 0.85 for low grafting yields, and approximately 1 for high grafting yields. Ultimately, this study demonstrated the possibility of using these thermoresponsive smart membranes in various applications.

Crystalline morphology and phase structure play a decisive role in determining the properties of polymer blends. In this research, biodegradable blends of poly(l-lactic acid) (PLLA) and poly(butylene succinate) (PBS) have been prepared by melt-extrusion and molded into specimens with rapid cooling. The crystalline morphology (e.g., crystallinity, crystal type and perfection) is manipulated by annealing the molded products from solid-state within a short time. This work emphasizes on the effects of annealing conditions on crystallization and properties of the blends, especially impact toughness and thermal stability. Phase-separation morphology with PBS dispersed particles smaller than 1 μm is created in the blends. The blend properties are successfully dictated by controlling the crystalline morphology. Increasing crystallinity alone does not ensure the enhancement of impact toughness. A great improvement of impact strength and heat resistance is achieved when the PLLA/PBS (80/20) blends are plasticized with 5% medium molecular-weight poly(ethylene glycol), and simultaneously heat-treated at a temperature close to the cold-crystallization of PLLA. The plasticized blend annealed at 92 °C for only 10 min exhibits ten-fold impact strength over the starting PLLA and slightly higher heat distortion temperature. The microscopic study demonstrates the fracture mechanism changes from crazing to shear yielding in this annealed sample.

This study explores the enhancement of electrical conductivity in polymer composites by incorporating carbon nanotubes (CNTs) into a co-continuous poly(lactic acid)/low-density polyethylene (PLA/LDPE) blend, creating a double percolation structure. Theoretical thermodynamic predictions indicate that CNTs preferentially localize in the LDPE phase. The percolation threshold of CNTs in the PLA/LDPE/CNT composites was 0.208 vol% (5.56 wt%), an 80% reduction compared to the LDPE/CNT composite, due to the double percolation structure. This thermodynamic migration of CNTs from PLA to LDPE significantly enhanced conductivity, achieving a 13.8-fold increase at a 7.5 wt% CNT loading compared to the LDPE/CNT composite. The localization of CNTs was driven by thermodynamic, kinetic, and rheological factors, with viscosity differences between PLA and LDPE causing dense CNT aggregation in LDPE. Initial contact of CNTs with PLA reduced aggregation, allowing PLA to infiltrate CNT aggregates during melt-mixing, which influenced the final morphology and electrical conductivity. These findings provide new insights into the fabrication of conductive polymer composites for force sensor applications.