Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/organo-modified montmorillonite (OMMT) nanocomposite films were prepared by melt compounding and cast-film extrusion at various loading rates, i.e. 1, 3 and 5 wt. %. The effect of OMMT on the biodegradability of produced PHBV nanocomposite films was investigated under controlled conditions in aqueous medium (20 C for 28 days) by monitoring the biochemical oxygen demand (BOD), and under laboratory-scale composting conditions (58 C for 70 days) by monitoring the weight and surface loss. The microstructural and macromolecular changes were monitored during the biodegradation process by means of scanning transmission electron microscopy (STEM), differential scanning calorimetry (DSC) and size exclusion chromatography (SEC) analysis. The initial microstructure of the nanocomposites samples exhibited an intercalated structure with a good clay/matrix affinity. BOD evolution in aqueous conditions as well as surface and weight loss in composting conditions indicated that the biodegradation rate of PHBV nanocomposites was lower than neat PHBV, which supports a barrier effect of OMMT. This was confirmed by the surface erosion observed through SEM accompanied by a significant decrease of the average molecular weight in the bulk of the films. Our results demonstrated that the biodegradation of PHBV and nanocomposite films occurred by combined hydrolytic and enzymatic processes, at the surface as well as in the bulk of the material. DSC analysis also revealed no change in the degree of crystallinity, which suggests that the amorphous and crystalline phases were degraded at same rate.
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