The hydrolytic and enzymatic degradation of polymer films of poly(3-hydroxybutyrate) (PHB) of different molecular mass and its copolymers with 3-hydroxyvalerate (PHBV) of different 3-hydroxyvalerate (3-HV) content and molecular mass, 3-hydroxy-4-methylvalerate (PHB4MV), and polyethylene glycol (PHBV-PEG) produced by the Azotobacter chroococcum 7B by controlled biosynthesis technique were studied under in vitro model conditions. The changes in the physicochemical properties of the polymers during their in vitro degradation in the pancreatic lipase solution and in phosphate-buffered saline for a long time (183 days) were investigated using different analytical techniques. A mathematical model was used to analyze the kinetics of hydrolytic degradation of poly(3-hydroxyaklannoate)s by not autocatalytic and autocatalytic hydrolysis mechanisms. It was also shown that the degree of crystallinity of some polymers changes differently during degradation in vitro. The total mass of the films decreased slightly up to 8–9% (for the high-molecular weight PHBV with the 3-HV content 17.6% and 9%), in contrast to the copolymer molecular mass, the decrease of which reached 80%. The contact angle for all copolymers after the enzymatic degradation decreased by an average value of 23% compared to 17% after the hydrolytic degradation. Young’s modulus increased up to 2-fold. It was shown that the effect of autocatalysis was observed during enzymatic degradation, while autocatalysis was not available during hydrolytic degradation. During hydrolytic and enzymatic degradation in vitro, it was found that PHBV, containing 5.7–5.9 mol.% 3-HV and having about 50% crystallinity degree, presents critical content, beyond which the structural and mechanical properties of the copolymer have essentially changed. The obtained results could be applicable to biomedical polymer systems and food packaging materials.

Five Poly(lactic acid) (PLA) film samples were analyzed to study the gas barrier behavior, thermal stability and mechanical performance for food packaging application. O2, CO2, N2, N2O, and C2H4 pure gases; Air; and Modified Atmosphere (MA, 79% N2O/21% O2) were used to analyze the influence of the chemical structure, storage temperature and crystalline phase on the gas barrier behavior. The kinetic of the permeation process was investigated at different temperatures, ranging from 5 °C to 40 °C. Annealing thermal treatment on the samples led to the crystalline percentage, influencing especially the gas solubility process. Thermal properties such as Tg and χc, and mechanical properties such as tensile strength and modulus were remarkably improved with surface PLA modification. A more pronounced reinforcing effect was noted in the case of metallization, as well as improved gas barrier performance. Tensile testing and tensile cycling tests confirmed the rigidity of the films, with about a 20% loss of elasticity after 25 cycles loading.

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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Compositions of polylactide (PLA) and poly(3-hydroxybutyrate) (PHB) thermoplastic polyesters originated from the nature raw have been obtained by blending under shear deformations and electrospinning methods in the form of films and nanofibers as well as unwoven nanofibrous materials, respectively. The degrees of crystallinity calculated on the base of melting enthalpies and thermal transition temperatures for glassy state, cold crystallization, and melting point for individual biopolymers and ternary polymer blends PLA-PHB- poly(ethyleneglycol) (PEG) have been evaluated. It has been shown that the mechanical properties of compositions depend on the presence of plasticizers PEG with different molar masses in interval of 400–1000. The experiments on the action of mold fungi on the films have shown that PHB is a fully biodegradable polymer unlike PLA, whereas the biodegradability of the obtained composites is determined by their composition. The sorption activity of PLA–PHB nanofibers and unwoven nanofibrous PLA–PHB composites relative to water and oil has been studied and the possibility of their use as absorbents in wastewater treatment from petroleum products has been demonstrated.

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Ultrathin fibrous materials based on natural bacterial polymer polyhydroxybutyrate (PHB) were prepared by the electrospinning method. Using scanning electron and optical microscopy techniques the macrophysical characteristics of the fibrous layer were determined and classified. The physicomechanical characteristics of the resultant materials and their changes caused by ozonation were determined as well. Structure formation in the ultrathin polyhydroxybutyrate fibers containing low antibacterial concentrations was studied. The effect of low concentrations of zinc tetraphenylporphyrin and iron(III) chloroteteraphenylporphyrin complexes on the structure of polyhydroxybutyrate-based ultrathin fibers was elucidated. Techniques used in the study were X-ray diffraction analysis, ESR spin probe method, differential scanning calorimetry, and optical and electron scanning microscopy. It was shown that addition of the metal porphyrin complexes caused changes in the degree of crystallinity and in the crystallite size of the PHB fibers, while the proportion of dense domains in the amorphous phase of the polymer fiber increased.

Nowadays, the development and research of nonwoven medical fibrous materials based on biopolymers is an area of a great practical interest. One of the most promising methods for producing nonwoven materials with a highly developed surface is electrospinning (ES). In this article, the possibility of efficient sterilization of ultrathin fibers based on polyhydroxybutyrate (PHB) by ozone treatment was considered. The purpose of this work was to select the most optimal morphology of nonwoven materials for medical purposes and to establish the correlation between the supramolecular structure and the physical properties of fibrous materials while under the influence of an ozone sterilization process.