This study investigates the effects of organic salts, including sodium citrate (SC), calcium citrate (CC), and calcium lactate (CL), on the structure–property–function relationships of thermoplastic starch/poly(butylene adipate-co-terephthalate) (TPS/PBAT) films for active packaging applications. TPS incorporated with organic salts was prepared via twin-screw extrusion, blended with PBAT, and further processed into blown films. The films were systematically characterized using 1H NMR, FTIR, and SEM, together with optical, mechanical, water vapor permeability, and antimicrobial evaluations against Staphylococcus aureus. The results revealed that SC primarily modulated hydrogen-bonding interactions within the starch matrix, resulting in improved structural homogeneity, balanced mechanical properties, and the highest antimicrobial activity among all formulations. In contrast, CL and CC promoted ionic crosslinking through Ca2+–starch interactions, leading to increased stiffness and Young’s modulus but reduced polymer chain mobility and limited release of active species, particularly in CC-containing systems. These differences in molecular interactions were consistent with variations in film microstructure, where SC-containing films exhibited more uniform morphologies, while calcium-based systems showed denser but less permeable structures. Furthermore, films containing SC and CL at appropriate concentrations achieved a favorable balance between transparency, water vapor barrier properties, and antimicrobial performance. Overall, this study provides new mechanistic insights into how monovalent and divalent organic salts govern intermolecular interactions, microstructure, and functional performance in TPS/PBAT systems. The findings highlight the critical role of additive type and concentration in designing biodegradable active packaging materials with tunable mechanical, barrier, and antimicrobial properties.
Roschhuk et al. (Fri,) studied this question.