Role of Chain Entanglements in the Electrospinning of Wheat Protein-Poly(Vinyl Alcohol) Blends

The aim of this investigation was to determine if the rapid solvent removal evaporation that occurs during electrospinning enabled the gluten protein and poly(vinyl alcohol) (PVOH) chains to remain at least partially entangled in the final product. Natural and synthetic biopolymer blends are known to phase separate in the melt. Differential scanning calorimetry (DSC) was used to test our hypothesis, which we achieved by systematically comparing the thermal profiles of the nonwoven fibrous sheets comprising: 1) 100% commercial wheat gluten, 2) 100% PVOH, and 3) the (75/25) wheat gluten/PVOH blend. The DSC scans of the two PVOH-containing, nonwoven fibrous sheets exhibited differences in the characteristics and positions of the melting peaks (T_m) of the PVOH crystalline phase, while the DSC scans of the nonwoven fibrous sheets comprising either 100% commercial wheat gluten or the wheat gluten/PVOH blend yielded neither a measurable glass transition temperature (T_g) nor a T_m. Energy dispersive spectroscopy (EDS) was used to compare the elemental compositions of the individual fibers with the compositions of the spherical domains found in the nonwoven fibrous mats. These scans revealed that the mineral matter found in commercial wheat gluten (roughly 1% by weight) had phase-separated from the bulk gluten protein as a result of electrospinning.     

Blends of Poly(hydroxybutyrate) and Poly(ethylene succinate) Prepared in the Presence of Samarium

Blends of the commercial biodegradable polymer poly(hydroxybutyrate) (PHB) with the oligomeric polyester poly(ethylene succinate) (PES) were prepared by melt processing in the presence of Sm(acac)₃. The occurrence of transesterification reactions during blend processing using the samarium catalyst was investigated. ¹H NMR analyses showed no evidence of transreactions, even using high content of catalyst (4 wt%), long reaction times and high temperatures (200°C). Under the drastic reaction conditions employed, chain degradation characterized by a significant decrease in the molecular weight (MW) of PHB has taken place. PHB/PES blends form immiscible systems in which the PHB crystallizes as large spherulites, but its crystallization is significantly influenced by the presence of PES, which does not crystallize at conditions in which the poly(hydroxyalkanoate) is crystallized.