Enhancing the Flexibility and Hydrophilicity of PLA via Polymer Blends: Electrospinning vs. Solvent Casting

Polylactic acid (PLA) is a biodegradable polymer with high tensile strength, high stiffness, and biocompatibility, but its brittleness and hydrophobicity limit its applications. This study aims to address these limitations by blending PLA with polycaprolactone (PCL) to enhance flexibility and with polyethylene oxide (PEO) to improve hydrophilicity. Unlike conventional approaches where PEO serves as a plasticizer, this study investigated PEO as a major blend component. Electrospinning and solvent casting, which differ in their solvent evaporation rates, were employed to fabricate thin films of neat PLA and PLA blends to examine their influence on mechanical and surface properties. Polymer solutions were prepared using a dichloromethane (DCM)/dimethylformamide (DMF) mixture known to enhance the electrospinning process. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) were used to investigate crystallinity of polymers and their interactions, while scanning electron microscopy (SEM) and atomic force microscopy (AFM) provided insights into phase separation and fiber morphology. Uniaxial tensile testing and water contact angle measurements were conducted to evaluate mechanical properties and surface properties, respectively. The results showed that electrospun PLA films exhibited higher elongation at break and ultimate strength but lower Young's modulus than solvent-cast PLA films. Electrospun films of PLA/PCL blends demonstrated improved elongation at break while retaining Young's modulus comparable to that of electrospun PLA films, unlike their solvent-cast counterparts. In contrast, PLA/PEO blends exhibited enhanced hydrophilicity in both processing methods but showed a marked reduction in mechanical properties. In summary, electrospun films consistently outperformed solvent-cast films in terms of flexibility and mechanical integrity, primarily due to their fibrous structure, suppressed phase separation, and reduced crystallinity. This study uniquely demonstrates that electrospinning enables the fabrication of phase-separated PLA/PEO blends with mechanical integrity despite PEO's inherent immiscibility with PLA and incompatibility in the solvent mixture. Furthermore, electrospinning proves to be an effective processing method for producing PLA blend films with enhanced flexibility and hydrophilicity without the need for plasticizers or compatibilizers.