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Actually, in order to replace traditional fossil-based polymers, many efforts are devoted to the design and development of new and high-performance bioplastics materials. Poly(hydroxy alkanoates) (PHAS) as well as polylactides are the main candidates as naturally derived polymers. The intention of the present study is to manufacture fully bio-based blends based on two polyesters: poly (3-hydroxybutyrate) (PHB) and polylactic acid (PLA) as real competitors that could be used to replace petrol polymers in packaging industry. Blends in the shape of films have been prepared by chloroform solvent cast solution methodology, at different PHB/PLA ratios: 1/0, 1/9, 3/7, 5/5, 0/1. A series of dynamic explorations have been performed in order to characterize them from a different point of view. Gas permeability to N2, O2, and CO2 gases and probe (TEMPO) electron spin resonance (ESR) analyses were performed. Blend surface morphology has been evaluated by Scanning Electron Microscopy (SEM) while their thermal behavior was analyzed by Differential Scanning Calorimetry (DSC) technique. Special attention was devoted to color and transparency estimation. Both probe rotation mobility and N2, O2, and CO2 permeation have monotonically decreased during the transition from PLA to PHB, for all contents of bio-blends, namely because of transferring from PLA with lower crystallinity to PHB with a higher one. Consequently, the role of the crystallinity was elucidated. The temperature dependences for CO2 permeability and diffusivity as well as for probe correlation time allowed the authors to evaluate the activation energy of both processes. The values of gas transport energy activation and TEMPO rotation mobility are substantially close to each other, which should testify that polymer segmental mobility determines the gas permeability modality.

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Abstract:The academic exploration and technology design of active packaging are coherently supplying innovative approaches for enhancing the quality and safety of food, as well as prolonging their shelf-life. With the object of comparison between two barrier materials, such as stable petrochemical polyurethane (PU), (BASF), and biodegradable natural poly(3-hydroxybutyrate) (PHB), (Biomer Co., Krailling, Germany), the study of antibacterial agent release has been performed. For the characterization of polymer surface morphology and crystallinity, the scanning electron microscopy (SEM), atomic force microscopy (AFM) and differential scanning calorimetry (DSC) were used respectively. The antimicrobial activity of chlorhexidine digluconate (CHD) has been estimated by the Bauer-Kirby Disk Diffusion Test. It was shown that the kinetic release profiles of CHD, as the active agent, in both polymers, significantly differed due to the superposition of diffusion and surface degradation in poly(3-hydroxybutyrate) (PHB). To emphasize the special transport phenomena in polymer packaging, the diffusivity modeling was performed and the CHD diffusion coefficients for the plane films of PU and PHB were further compared. The benefit of active biodegradable packaging on the base of PHB is discussed.