PLA, PBS, and PBAT Biocomposites—Part A: Matrix–Filler Interactions with Agro-Industrial Waste Fillers (Brewer’s Spent Grain, Orange Peel) and Their Influence on Thermal, Mechanical, and Water Sorption Properties

Plastic pollution, largely driven by packaging waste, calls for sustainable alternatives. This study investigates biodegradable thermoplastic biocomposites based on PLA, PBS, and PBAT, incorporating 10 wt.% of agro-industrial filler-brewers' spent grain (BSG) and orange peel (OP) without compatibilization. The biocomposites were produced by melt extrusion followed by thermo-compression. A full factorial design was implemented to assess matrix-filler interactions and compare biocomposites to pure polymer fragments. OP particles, smaller and rougher than BSG, exhibited a higher specific surface area, influencing composite morphology and behavior. The OP slightly plasticized PLA, possibly due to volatile release during processing, whereas BSG increased stiffness in PBS and PBAT. Both fillers reduced mechanical strength, especially in PLA, due to limited interfacial adhesion, and significantly decreased PLA's thermal stability. The addition of fillers also increased water sorption and modified the sorption kinetics of the three main modes (Langmuir-type, Henry's law sorption, and water molecule clustering), as well as the values of the half-sorption diffusion coefficients (D₁ and D₂), with notable differences between the OP and BSG linked to their structure and composition. These findings provide a better understanding of structure-property relationships in biodegradable composites and highlight their potential for sustainable packaging and other industrial applications.