Binary Biopolymer Blends: Influence of Mixing Procedure on Mechanical Properties of Polymer Thin Films

Polylactic acid (PLA) is one of the most promising bio-based and biodegradable polymers, yet its inherent brittleness limits its application in flexible film products. This study compares three mixing strategies, applied as four sample series, to improve the mechanical performance of PLA-based binary blends: (1) single-pass melt blending with poly(butylene adipate-co-terephthalate) (PBAT) or poly(butylene succinate) (PBS) at 10, 20, and 30 wt%; (2) addition of poly(ethylene glycol) (PEG 4000 or PEG 20000) as a plasticizer/compatibilizer at 1, 3, and 5 wt%; (3) double melt processing of PLA/PBAT and PLA/PBS blends. Thin films were characterised by tensile testing, differential scanning calorimetry (DSC), FTIR, SEM and contact angle measurements. Double processing emerged as the most effective approach, yielding elongation at break values up to approximately 137% for 70PLA/30PBAT blends, compared to 16.9% for the equivalent single-processed samples. Relative to the single-processed controls, double processing raised elongation at break by approximately 712% for 70PLA/30PBAT and 1201% for 70PLA/30PBS, and by 98% (80PLA/20PBAT), 175% (80PLA/20PBS) and 278% (90PLA/10PBAT); the latter three increases were statistically significant (p < 0.05). By contrast, PEG addition changed maximum stress by at most about 18% and never raised elongation at maximum stress above 6%. Two-way ANOVA confirmed that blend ratio was a significant factor for maximum stress (p < 0.001) whereas PEG molecular weight was not (p > 0.10). PEG addition produced moderate improvements in tensile stress, but did not replicate the ductility enhancement observed after reprocessing. DSC data confirmed a decrease in the glass transition temperature (Tg) and altered crystallisation behaviour in double-processed samples, consistent with improved interfacial compatibility. Contact angle results showed broadly similar surface wettability across all series, pointing to processing history, rather than surface chemistry, as the key variable governing final mechanical behaviour in these blends.