Abstract
The purpose of the present work was to gain a fundamental understanding of how the composition and physico-chemical properties affect the rheology, morphology, miscibility, and thermal stability of poly(lactic acid) (PLA)—poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) biopolymer blends obtained by melt mixing. First, restricted processing conditions were chosen, due to the inherent thermal degradation of PHBV, as proven by rheological dynamic time sweep (DTS) measurements and size-exclusion chromatography (SEC). Based on this, the composition dependence of the blends was investigated using small-amplitude oscillatory shear rheology (SAOS), and the results were confirmed by scanning electron microscopy (SEM) analysis. Subsequently, the changes in glass transition temperatures (Tgs) from the molten to the solid state, as observed by DMA and DSC, were verified by coupling SAOS to dielectric relaxation spectroscopy (DRS). Herein, the thermo-rheological complexity of PLA/PHBV blends in the melt was revealed, especially for PLA-rich blends. Irregularly structured morphologies, caused by highly mismatched viscoelastic properties, illustrated the degree of partial miscibility. Moreover, the thermo-rheological complexity appeared in the molten state of the asymmetric PLA-rich phases could be correlated to the crystal-amorphous interfacial MWS polarization, because of the locally-induced phase separation and heterogeneity, and owing to the differences in their crystallization properties during cooling. The miscibility also suffered from the lower thermal stability of PLA and the even more unstable PHBV. Nevertheless, the melt-induced degradation process of the PLA/PHBV blends seemed to be responsible for some of the in situ self-compatibilization and plasticization mechanisms. As a result, the miscibility and thermo-rheological simplicity were improved for the intermediate and PHBV-rich compositions at low temperatures, since their properties were, to a large extent, governed by the significant degradation of PHBV. The present findings should increase the understanding of morphological changes in PLA/PHBV blends and help control their micro/nanostructure.
Subject
Polymers and Plastics,General Chemistry