Structural Characterization and Segmental Dynamics Evaluation in Eco-Friendly Polymer Electrospun Fibers Based on Poly(3-hydroxybutyrate)/Polyvinylpyrrolidone Blends to Evaluate Their Sustainability

Ultrafine fibers from poly(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) and their blends with different component ratios in the range of 0/100 to 100/0 wt.% were obtained, and their structure and dynamic properties were studied. The polymers were obtained via electrospinning in solution mode. The structure, morphology, and segmental dynamic behavior of the fibers were determined using optical microscopy, SEM, EPR, DSC, and IR spectroscopy. The low-temperature maximum on the DSC endotherms provided information on the state of the PVP hydrogen bond network, which made it possible to determine the enthalpies of thermal destruction of these bonds. The PHB/PVP fiber blend ratio significantly affected the structural and dynamic parameters of the system. Thus, at low concentrations of PVP (up to 9%) in the structure of ultra-fine fibers, the distribution of this polymer occurs in the form of tiny particles, which are crystallization centers, which causes a significant increase in the degree of crystallinity (χ) activation energy (Eact) and slowing down of molecular dynamics (τ). At higher concentrations of PVP, loose interphase layers were formed in the system, which caused a decrease in these parameters. The strongest changes in the concentration of hydrogen bonds occurred when PVP was added to the composition from 17 to 50%, which was due to the formation of intermolecular hydrogen bonds both in PVP and during the interaction of PVP and PHB. The diffusion coefficient of water vapor in the studied systems (D) decreased as the concentration of glassy PVP in the composition increased. The concentration of the radical decreased with an increase in the proportion of PVP, which can be explained by the glassy state of this polymer at room temperature. A characteristic point of the 50/50% mixture component ratio was found in the region where an inversion transition of PHB from a dispersion material to a dispersed medium was assumed. The conducted studies made it possible for the first time to conduct a comprehensive analysis of the effect of the component ratio on the structural and dynamic characteristics of the PHB/PVP fibrous material at the molecular scale. © 2025 Elsevier B.V., All rights reserved.