The present study describes the preparation and characterization of binary and ternary blends based on polylactide (PLA) with poly(ε-caprolactone) (PCL) and thermoplastic starch (TPS) to develop fully compostable plastics with improved ductility and toughness. To this end, PLA was first melt-mixed in a co-rotating twin-screw extruder with up to 40 wt % of different PCL and TPS combinations and then shaped into pieces by injection molding. The mechanical, thermal, and thermomechanical properties of the resultant binary and ternary blend pieces were analyzed and related to their composition. Although the biopolymer blends were immiscible, the addition of both PCL and TPS remarkably increased the flexibility and impact strength of PLA while it slightly reduced its mechanical strength. The most balanced mechanical performance was achieved for the ternary blend pieces that combined high PCL contents with low amounts of TPS, suggesting a main phase change from PLA/TPS (comparatively rigid) to PLA/PCL (comparatively flexible). The PLA-based blends presented an “island-and-sea” morphology in which the TPS phase contributed to the fine dispersion of PCL as micro-sized spherical domains that acted as a rubber-like phase with the capacity to improve toughness. In addition, the here-prepared ternary blend pieces presented slightly higher thermal stability and lower thermomechanical stiffness than the neat PLA pieces. Finally, all biopolymer pieces fully disintegrated in a controlled compost soil after 28 days. Therefore, the inherently low ductility and toughness of PLA can be successfully improved by melt blending with PCL and TPS, resulting in compostable plastic materials with a great potential in, for instance, rigid packaging applications.
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