Sustainable micro and nano additives for controlling the migration of a biobased plasticizer from PLA-based flexible films

Plasticized poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blend-based films containing chitin nanofibrils (CN) and calcium carbonate were prepared by extrusion and compression molding. On the basis of previous studies, processability was controlled by the use of a few percent of a commercial acrylic copolymer acting as melt strength enhancer and calcium carbonate. Furthermore, acetyl n-tributyl citrate (ATBC), a renewable and biodegradable plasticizer (notoriously adopted in PLA based products) was added to facilitate not only the processability but also to increase the mechanical flexibility and toughness. However, during the storage of these films, a partial loss of plasticizer was observed. The consequence of this is not only correlated to the change of the mechanical properties making the films more rigid but also to the crystallization and development of surficial oiliness. The effect of the addition of calcium carbonate (nanometric and micrometric) and natural nanofibers (chitin nanofibrils) to reduce/control the plasticizer migration was investigated. The prediction of plasticizer migration from the films' core to the external surface was carried out and the diffusion coefficients, obtained by regression of the experimental migration data plotted as the square root of time, were evaluated for different blends compositions. The results of the diffusion coefficients, obtained thanks to migration tests, showed that the CN can slow the plasticizer migration. However, the best result was achieved with micrometric calcium carbonate while nanometric calcium carbonate results were less effective due to favoring of some bio polyesters' chain scission. The use of both micrometric calcium carbonate and CN was counterproductive due to the agglomeration phenomena that were observed.