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In the context of sustainable materials, this study explores the effects of accelerated weathering testing and bacterial biodegradation on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/rapeseed microfiber biocomposites. Accelerated weathering, simulating outdoor environmental conditions, and bacterial biodegradation, representing natural degradation processes in soil, were employed to investigate the changes in the mechanical, thermal and morphological properties of these materials during its post-production life cycle. Attention was paid to the assessment of the change of structural, mechanical and calorimetric properties of alkali and N-methylmorpholine N-oxide (NMMO)-treated rapeseed microfiber (RS)-reinforced plasticized PHBV composites before and after accelerated weathering. Results revealed that accelerated weathering led to an increase in stiffness, but a reduction in tensile strength and elongation at break, of the investigated PHBV biocomposites. Additionally, during accelerated weathering, the crystallinity of PHBV biocomposites increased, especially in the presence of RS, due to both the hydrolytic degradation of the polymer matrix and the nucleating effect of the filler. It has been observed that an increase in PHBV crystallinity, determined by DSC measurements, correlates with the intensity ratio I1225/1180 obtained from FTIR-ATR data. The treatment of RS microfibers increased the biodegradation capability of the developed PHBV composites, especially in the case of chemically untreated RS. All the developed PHBV composites demonstrated faster biodegradation in comparison to neat PHBV matrix.
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The current research is devoted to the investigation of the plasticization of polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-hydroxyvalerate (PHBV) with triethyl citrate (TEC). Three different PHB or PHBV-based systems with 10, 20, and 30 wt.% of TEC were prepared by two-roll milling. The effect of TEC on the rheological, thermal, mechanical, and calorimetric properties of the developed compression-molded PHB and PHBV-based systems was determined. It was revealed that the addition of TEC significantly influenced the melting behavior of both polyhydroxyalkanoates (PHA), reducing their melting temperatures and decreasing viscosities. It was also revealed that all the investigated systems demonstrated less than 2% weight loss until 200 °C and rapid degradation did not occur until 240-260 °C in an oxidative environment. Apart from this, a remarkable increase (ca 2.5 times) in ultimate tensile deformation εB was observed by increasing the amount of TEC in either PHB or PHBV. A concomitant, considerable drop in ultimate strength σB and modulus of elasticity E was observed. Comparatively, the plasticization efficiency of TEC was greater in the case of PHBV.
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In this study, propolis additives provide antibacterial and antifungal effects that prolong the product's shelf life. The aim of the study is to obtain homogeneous fiber membranes of polyvinyl alcohol and propolis by the electrospinning method and to evaluate their suitability for food packaging. Three propolis extracts are used in the study-water, ethyl alcohol, and glycerin-based. The membranes' morphology and fiber diameter distribution, tensile deformation, air permeability, thermogravimetric analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, and microbiological tests (Listeria monocytogenes, Salmonella enteritidis, Escherichia coli) were analyzed for electrospun samples. The results of the study show that propolis extracts are incorporated into membranes and the additive provides an antimicrobial effect with the contact surface. The obtained membranes are breathable: gas exchange can be controlled by using a material of appropriate thickness (air permeability coefficient is 0.046 and 0.276 mm/s). The mechanical properties of membranes are affected by moisture, but tensile strength can be improved with thermal post-processing at 100 °C. The propolis-containing fibers' diameters are from 293 ± 8 to 664 ± 11 nm. Depending on membranes' demonstrated properties, it can be concluded that the composites have the potential to increase the shelf life of fresh fruits and berries.
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Películas Comestibles , Própolis , Própolis/química , Embalaje de Alimentos/métodos , Antibacterianos/farmacología , Antibacterianos/química , Resistencia a la TracciónRESUMEN
The aim of the study was to assess the usefulness of agricultural biomass residues as reinforcement in recycled polymer matrices. In this study, recycled polypropylene and high-density polyethylene composites (rPPPE) filled with three types of biomass residues, sweet clover straws (SCS), buckwheat straws (BS) and rapeseed straws (RS), are presented. The effects of the fiber type and the fibers content on the rheological behavior, mechanical properties (including tensile, flexural and impact strength), thermal stability and moisture absorbance were determined, in addition to morphological analysis. It was revealed that the addition of SCS, BS or RS increased the materials' stiffness and strength. The reinforcement effect increased as the loading of the fibers was increased, especially for BS composites in the flexural test. After the moisture absorbance test, it was found that the reinforcement effect slightly increased for the composites with 10% fibers but decreases with 40% fibers. The results highlight that the selected fibers are a feasible reinforcement for recycled polyolefin blend matrices.
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The current research is devoted to the research of potential catalysts for the two-component silyl-terminated prepolymer/epoxy resin system. The catalyst system must catalyze the prepolymer of the opposite component while not curing the prepolymer in the component in which the catalyst is located. Mechanical and rheological characterization of the adhesive was performed. The results of the investigation showed that certain alternative catalyst systems, which are less toxic, may be used instead of traditional catalysts for individual systems. Two-component systems, obtained by using these catalysts systems, cure in an acceptable time scale and demonstrate relatively high tensile strength and deformation values.
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The reduction of tissue cytotoxicity and the improvement of cell viability are of utmost significance, particularly in the realm of green chemistry. Despite substantial progress, the threat of local infections remains a concern. Therefore, hydrogel systems that provide mechanical support and a harmonious balance between antimicrobial efficacy and cell viability are greatly needed. Our study explores the preparation of physically crosslinked, injectable, and antimicrobial hydrogels using biocompatible hyaluronic acid (HA) and antimicrobial ε-polylysine (ε-PL) in different weight ratios (10 wt% to 90 wt%). The crosslinking was achieved by forming a polyelectrolyte complex between HA and ε-PL. The influence of HA content on the resulting HA/ε-PL hydrogel physicochemical, mechanical, morphological, rheological, and antimicrobial properties was evaluated, followed by an inspection of their in vitro cytotoxicity and hemocompatibility. Within the study, injectable, self-healing HA/ε-PL hydrogels were developed. All hydrogels showed antimicrobial properties against S. aureus, P. aeruginosa, E. coli, and C. albicans, where HA/ε-PL 30:70 (wt%) composition reached nearly 100% killing efficiency. The antimicrobial activity was directly proportional to ε-PL content in the HA/ε-PL hydrogels. A decrease in ε-PL content led to a reduction of antimicrobial efficacy against S. aureus and C. albicans. Conversely, this decrease in ε-PL content in HA/ε-PL hydrogels was favourable for Balb/c 3T3 cells, leading to the cell viability of 152.57% for HA/ε-PL 70:30 and 142.67% for HA/ε-PL 80:20. The obtained results provide essential insights into the composition of the appropriate hydrogel systems able to provide not only mechanical support but also the antibacterial effect, which can offer opportunities for developing new, patient-safe, and environmentally friendly biomaterials.
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According to scientific research from different countries, crumb rubber obtained from end-of-life tires (ELT) during processing can improve the properties of the asphalt mixture, thereby extending the service life of the road surface. This paper presents the modification of bitumen with industrial rubber waste. The modification of bitumen for roads is considered one of the most suitable and popular approaches. This research paper describes the details of using different types of crumb rubber as bitumen modifiers. The modified bitumen's main physical and mechanical characteristics were determined after conventional tests: penetration and ductility, softening point, and Fraas brittleness point. In order to obtain a rubber-asphalt concrete mixture with improved performance characteristics, the viscoelastic and rheological properties of rubber-bitumen binders and their comparison with polymer-bitumen binders were also studied. The research results show that with increasing temperature, the values of viscosity, shear stress and complex shear modulus of all studied bitumen systems decrease, the values of the phase shift angle increase, and the size of the rubber particles has a greater influence on the properties of bitumen systems.
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This work is devoted to the fabrication of p-type polyvinyl alcohol (PVA)-based flexible thermoelectric composites using multiwall carbon nanotubes-antimony telluride (MWCNT-Sb2Te3) hybrid filler, the study of the thermoelectrical and mechanical properties of these composites, and the application of these composites in two types (planar and radial) of thermoelectric generators (TEG) in combination with the previously reported PVA/MWCNT-Bi2Se3 flexible thermoelectric composites. While the power factors of PVA/MWCNT-Sb2Te3 and PVA/MWCNT-Bi2Se3 composites with 15 wt.% filler were found to be similar, the PVA/MWCNT-Sb2Te3 composite with 25 wt.% filler showed a ~2 times higher power factor in comparison with the PVA/MWCNT-Bi2Se3 composites with 30 wt.% filler, which is attributed to its reduced electrical resistivity. In addition, developed PVA/MWCNT-Sb2Te3 composites showed a superior mechanical, electrical, and thermoelectric stability during 100 consequent bending cycles down to a 3 mm radius, with insignificant fluctuations of the resistance within 0.01% of the initial resistance value of the not bent sample. Demonstrated for the first time, 2-leg TEGs composed from p-type PVA/MWCNT-Sb2Te3 and n-type PVA/MWCNT-Bi2Se3 composites showed a stable performance under different external loads and showed their potential for applications involving low temperature gradients and power requirements in the range of nW.
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Current research is devoted to the investigation of spelt husk (SH) and nanoclay-modified compatibilised polypropylene (PP) binary and ternary composites for injection-moulding applications. PP composites were obtained using twin-screw extrusion. The content of mechanically milled SH microfiller with aspect ratio within 2 and 6 was fixed at 40 wt.%, whereas the amount of nanoclay functional filler in the polypropylene matrix was changed in the range from 0.5 to 5 wt.%. Nanoclay filler was introduced in the polypropylene matrix either in the form of nanoclay powder (C) or as a masterbatch (M). Regular distribution of the clay nanofiller within the polymer matrix has been observed, disregarding its form and concentration. The effects of the individual or combined addition of SH microreinforcement and nanoclay fillers on the rheological, mechanical, calorimetric, and thermal properties of the developed PP composites were investigated. It is revealed that the addition of the nanoclay fillers insignificantly influences the viscosity of both PP nanocomposites and hybrid composites with SH. Additionally, for PP nanocomposites, remarkable increases in tensile and flexural modules and strength are observed by maintaining considerable ultimate deformations, mainly in the case of M-containing systems. Concomitantly, because of the addition of the nanoclay filler, the improvement in thermal stability of PP nanocomposites and PP hybrid composites with SH is observed. As a result of SH addition, considerable increases in tensile and flexural modules are also observed. Results of the research demonstrate the potential of the use of natural materials (agricultural residues and clay minerals) for the development of PP composites with increased stiffness and thermal properties.
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The birch (Betula spp.) outer bark is a valuable product rich in betulin. After removal of betulin extractives, suberin containing tissues are left. Suberin is a biopolyester built from α,ω-bifunctional fatty acids (suberinic acids), which after depolymerization together with lignocarbohydrate complex is a potential adhesive as a side-stream product (residue) from obtaining suberinic acids for polyol synthesis. In this work, we studied the utilization possibilities in particleboards of the said residue obtained by depolymerization in four different solvents (methanol, ethanol, isopropanol and 1-butanol). The adhesives were characterised by chemical (acid number, solubility in tetrahydrofuran, epoxy and ash content) and instrumental analytical methods (SEC-RID, DSC, TGA and FTIR). Based on the results of mechanical characteristics, ethanol was chosen as the most suitable depolymerization medium. The optimal hot-pressing parameters for particleboards were determined using the design of experiments approach: adhesive content 20 wt%; hot-pressing temperature 248 °C, and hot-pressing time 6.55 min.
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The current research is devoted to the investigation of the influence of a secondary amine compatibilizer and customized additive package on the tensile, rheological and adhesive properties of a Silyl-terminated polyether (SIL)/Epoxy resin (EP) model and completed two-component systems. A SIL/EP model and completed two-component systems were developed over a broad range of the both pre-polymer ratios (90/10-30/70 wt.-to-wt%). Additive packages of the components A and B were designed to prevent premature polycondensation of the respective pre-polymers (including suitable catalysts for each of the pre-polymers, as well as vinyltrimetoxysilane as a drying agent for moisture control), to ensure easy processing and stable performance of the system. Results of the investigation testify that the values of the tensile strength and Shore-A hardness of the compatibilized systems are higher in comparison to unmodified ones. In the presence of the additive package, a further improvement of tensile strength and tensile strain values is observed for SIL-rich compositions (SIL content above 70 wt%), whereas at lower SIL concentrations, the reinforcing effect is considerably reduced. In respects to adhesion properties, the highest values to a broad range of substrates with different surface polarities are observed at the SIL/EP range from 80/20 to 50/50 wt.-to-wt%.
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This research is devoted to the fabrication of polyvinyl alcohol (PVOH) based n-type thermoelectric composites with innovative hybrid bismuth selenide-multiwalled carbon nanotube (Bi2Se3-MWCNT) fillers for application in flexible thermoelectric devices. Hybrid fillers were synthesized by direct deposition of Bi2Se3 on multiwalled carbon nanotubes using a physical vapor deposition method, thus ensuring direct electrical contact between the carbon nanotubes and Bi2Se3. The Seebeck coefficient of prepared PVOH/Bi2Se3-MWCNT composites was found to be comparable with that for the Bi2Se3 thin films, reaching -100 µV·K-1 for the composite with 30 wt.% filler, and fluctuations of the resistance of these composites did not exceed 1% during 100 repetitive bending cycles down to 10 mm radius, indicating the good mechanical durability of these composites and proving their high potential for application in flexible thermoelectrics. In addition, other properties of the fabricated composites that are important for the use of polymer-based materials such as thermal stability, storage modulus and linear coefficient of thermal expansion were found to be improved in comparison with the neat PVOH.
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Developing polyols derived from natural sources and recycling materials attracts great interest for use in replacing petroleum-based polyols in polyurethane production. In this study, rigid polyurethane (PUR) foams with various isocyanate indices were obtained from polyols based on rapeseed oil and polyethylene terephthalate (RO/PET). The various properties of the prepared PUR foams were investigated, and the effect of the isocyanate index was evaluated. The closed-cell content and water absorption were not impacted by the change of the isocyanate index. The most significant effect of increasing the isocyanate index was on the dimensional stability of the resulting foams. This is due to the increased crosslink density, as evidenced by the increased formation of isocyanurate and increase of the glass transition temperature. Additionally, the influence on compression strength, modulus, and long-term thermal conductivity were evaluated and compared with reference PUR foams from commercially available polyols. Rigid PUR foams from RO/PET polyol were found to be competitive with reference materials and could be used as thermal insulation material.
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Incorporating enzymes into calcium alginate beads is an effective method to immobilise them and to preserve, at the same time, their catalytic activity. Sodium alginate was mixed with Aspergillus ficuum tannase in aqueous solution, and tannase-loaded calcium alginate beads were prepared using a simple droplet-based microfluidic system. Extensive experimental analysis was carried out to characterise the samples. Microscopic imaging revealed morphological differences between the surfaces of bare alginate matrix and tannase-loaded alginate beads. Thermal analysis allowed assessing the hydration contents of alginate and revealed the presence of tannase entrapped in the loaded beads, which was confirmed by vibrational spectroscopy. X-ray diffraction allowed us to conclude that alginate of tannase-loaded beads is not crystalline, which would make them suitable as carriers for possible controlled release. Moreover, they could be used in food applications to improve tea quality or clarify juices.
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Alginatos/química , Hidrolasas de Éster Carboxílico/química , Enzimas Inmovilizadas/química , Microesferas , Aspergillus/enzimología , Ácido Glucurónico/química , Ácidos Hexurónicos/química , Microscopía , Espectroscopía Infrarroja por Transformada de Fourier , Temperatura , Termogravimetría , Difracción de Rayos XRESUMEN
A polymer nanocomposite was produced by ultrasonic-assisted dispersion of multiwalled carbon nanotubes (MWCNTs) in a polycarbonate matrix using p-xylene and dichloromethane as the solvents. The filler loading was varied from 1 to 3 wt % in order to examine the effect of MWCNTs on the structure and properties of the composites. The nanocomposites were characterized by DSC, DTA, TGA, UV-vis, FTIR and Raman spectroscopy to evaluate the changes induced by the filler in the polymer matrix. UV-vis, FTIR and Raman spectroscopy measurements confirmed the presence of the dispersed phase in the composite films, while TGA and DSC analysis of the nanocomposites revealed enhanced thermal stability and decreased crystallinity, respectively, as compared to the neat polymer. The proposed composites can find application in a number of everyday products where polycarbonate is the base polymer.