Biobased Resin for Sustainable Stereolithography: 3D Printed Vegetable Oil Acrylate Reinforced with Ultra-Low Content of Nanocellulose for Fossil Resin Substitution.

The use of biobased materials in additive manufacturing is a promising long-term strategy for advancing the polymer industry toward a circular economy and reducing the environmental impact. In commercial 3D printing formulations, there is still a scarcity of efficient biobased polymer resins. This research proposes vegetable oils as biobased components to formulate the stereolithography (SLA) resin. Application of nanocellulose filler, prepared from agricultural waste, remarkably improves the printed material's performance properties. The strong bonding of nanofibrillated celluloses' (NFCs') matrix helps develop a strong interface and produce a polymer nanocomposite with enhanced thermal properties and dynamical mechanical characteristics. The ultra-low NFC content of 0.1-1.0 wt% (0.07-0.71 vol%) was examined in printed samples, with the lowest concentration yielding some of the most promising results. The developed SLA resins showed good printability, and the printing accuracy was not decreased by adding NFC. At the same time, an increase in the resin viscosity with higher filler loading was observed. Resins maintained high transparency in the 500-700 nm spectral region. The glass transition temperature for the 0.71 vol% composition increased by 28°C when compared to the nonreinforced composition. The nanocomposite's stiffness has increased fivefold for the 0.71 vol% composition. The thermal stability of printed compositions was retained after cellulose incorporation, and thermal conductivity was increased by 11%. Strong interfacial interactions were observed between the cellulose and the polymer in the form of hydrogen bonding between hydroxyl and ester groups, which were confirmed by Fourier-transform infrared spectroscopy. This research demonstrates a great potential to use acrylated vegetable oils and nanocellulose fillers as a feedstock to produce high-performance resins for sustainable SLA 3D printing.

Electrospun Fibrous Materials with Propolis Extracts for Edible Food Packagings.

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.

Effect of Electrode Type on Electrospun Membrane Morphology Using Low-Concentration PVA Solutions.

Electrospun polymer nanofiber materials have been studied as basic materials for various applications. Depending on the intended use of the fibers, their morphology can be adjusted by changing the technological parameters, the properties of the spinning solutions, and the combinations of composition. The aim of the research was to evaluate the effect of electrode type, spinning parameters, polymer molecular weight, and solution concentration on membranes morphology. The main priority was to obtain the smallest possible fiber diameters and homogeneous electrospun membranes. As a result, five electrode types were selected, the lowest PVA solution concentration for stable spinning process was detected, spinning parameters for homogenous fibers were obtained, and the morphology of electrospun fiber membranes was analyzed. Viscosity, conductivity, pH, and density were evaluated for PVA polymers with five different molecular weights (30-145 kDa) and three concentration solutions (6, 8, and 10 wt.%). The membrane defects and fiber diameters were compared as a function of molecular weight and electrode type. The minimum concentration of PVA in the solution allowed more additives to be added to the solution, resulting in thinner diameters and a higher concentration of the additive in the membranes. The molecular weight, concentration, and electrode significantly affected the fiber diameters and the overall quality of the membrane.

Propolis Integration Methods into Solutions for Highly Loaded Propolis Fibers by Needleless Electrospinning.

A load-bearing matrix filled with biologically active compounds is an efficient method for transporting them to the target location. Bee-made propolis has long been known as a natural product with antibacterial and antiviral, anti-inflammatory, antifungal properties, and anti-oxidative activity. The aim of the research is to obtain stable propolis/PVA solutions and produce fibers by electrospinning. To increase propolis content in fibers as much as possible, various types of propolis extracts were used. As a result of the research, micro- and nano-fiber webs were obtained, the possible use of which have biomedical and bioprotective applications. All used materials are edible and safe for humans, and fiber webs were prepared without using any toxic agent. This strategy overcomes propolis processing problems due to limitations to its solubility. The integration of different combinations of extracts allows more than 73 wt% of propolis to be incorporated into the fibers. The spinning solution preparation method was adapted to each type of propolis, and by combining the methods, solutions with different propolis extracts were obtained. Firstly, the total content of flavonoids in the propolis extracts was determined for the assessment and prediction of bioactivity. The properties of the extracts relevant for the preparation of electrospinning solutions were also evaluated. Secondly, the most appropriate choice of PVA molecular weight was made in order not to subject the propolis to too high temperatures (to save resources and not reduce the bioactivity of propolis) during the solution preparation process and to obtain fibers with the smallest possible diameter (for larger surface-to-volume ratios of nanofibers and high porosity). Third, electrospinning solutions were evaluated (viscosity, pH, conductivity and density, shelf life) before and after the addition of propolis to predict the maximum propolis content in the fibers and spinning stability. Each solution combination was spun using a cylindrical type electrode (suitable for industrial production) and tested for a stable electrospinning process. Using adapted solution-mixing sequences, all the obtained solutions were spun stably, and homogeneous fibers were obtained without major defects.