The Effect of Citrate Plasticisers TBC and ATBC on Biobased and Sustainable PHB-Based Polymer Blends

The development of fully biodegradable poly(3-hydroxybutyrate) (PHB)-based materials with improved mechanical performance remains a major challenge due to the limited ductility and processability of this highly crystalline polymer. Blending and plasticisation are viable strategies to enhance PHB toughness; however, the interactions governing polymer–plasticiser compatibility and their impact on structure–property relationships remain not fully understood. In this work, the compatibility and plasticisation mechanisms of two citrate-based plasticisers, tributyl citrate (TBC) and acetyl tributyl citrate (ATBC), were systematically investigated in biodegradable blends based on PHB, polylactic acid (PLA), and poly(butylene adipate-co-terephthalate) (PBAT). Polymer–plasticiser affinity was evaluated through Hansen Solubility Parameters and interaction radius, which indicated good compatibility of PHB with both plasticisers and a stronger affinity for ATBC. Differential scanning calorimetry showed that citrate plasticisers reduced the glass transition temperature, modified crystallisation kinetics, and altered the crystalline morphology of the blends. Dynamic mechanical analysis confirmed the reduction in the glass transition temperature of PHB–PLA systems, which is in agreement with the DSC results. Migration experiments showed equilibrium after approximately 72 h, with PHB–PLA blends exhibiting better plasticiser retention than PHB–PBAT systems. TBC consistently showed higher migration than ATBC, in line with its lower molecular weight and higher volatility. Mechanical testing demonstrated that plasticisation efficiency strongly depended on blend composition: TBC was more effective in enhancing ductility in PHB–PLA blends, whereas ATBC performed better in PHB–PBAT systems. It was also highlighted that the plasticisers had a remarkable ability to substantially increase the ductility of the blends compared with their unplasticised counterparts, as reflected by the pronounced decrease in stiffness and the marked increase in elongation at break. SEM analysis of tensile fracture surfaces evidenced a brittle failure mode for PHB–PLA blends, whereas PHB–PBAT systems exhibited a ductile fracture mode with fibrillar features and clear signs of phase separation. Finally, thermogravimetric analysis showed no appreciable thermal degradation within the processing temperature window used for mixing and hot pressing, confirming the thermal stability of the materials under the selected conditions. These findings establish clear correlations between thermodynamic compatibility, migration behaviour, thermal properties, fracture mechanisms, and mechanical performance, providing useful guidelines for the design of citrate-plasticised PHB-based biodegradable materials.