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Grape seeds (GS), wine lees (WL), and grape pomace (GP) are common winery by-products, used as bio-fillers in this research with two distinct biopolymer matrices—poly(butylene adipate-co-terephthalate) (PBAT) and polybutylene succinate (PBS)—to create fully bio-based composite materials. Each composite included at least 30 v% bio-filler, with a sample reaching 40 v%, as we sought to determine a composition that could be economically and environmentally effective as a substitute for a pure biopolymer matrix. The compounding process employed a twin-screw extruder followed by an injection molding procedure to fabricate the specimens. An acetylation treatment assessed the specimen’s efficacy in enhancing matrix–bio-filler affinity, particularly for WL and GS. The fabricated bio-composites underwent an accurate characterization, revealing no alteration in thermal properties after compounding with bio-fillers. Moreover, hygroscopic measurements indicated increased water-affinity in bio-composites compared to neat biopolymer, most significantly with GP, which exhibited a 7-fold increase. Both tensile and dynamic mechanical tests demonstrated that bio-fillers not only preserved, but significantly enhanced, the stiffness of the neat biopolymer across all samples. In this regard, the most promising results were achieved with the PBAT and acetylated GS sample, showing a 162% relative increase in Young’s modulus, and the PBS and WL sample, which exhibited the highest absolute values of Young’s modulus and storage modulus, even at high temperatures. These findings underscore the scientific importance of exploring the interaction between bio-fillers derived from winery by-products and three different biopolymer matrices, showcasing their potential for sustainable material development, and advancing polymer science and bio-sourced material processing. From a practical standpoint, the study highlighted the tangible benefits of using by-product bio-fillers, including cost savings, waste reduction, and environmental advantages, thus paving the way for greener and more economically viable material production practices.

The present work aimed to prepare novel bio-based composites by adding fillers coming from agro-wastes to an acrylate epoxidized soybean oil (AESO) resin, using liquid crystal display (LCD) 3D printing. Different photocurable formulations were prepared by varying the reactive diluents, iso-bornyl methacrylate (IBOMA) and tetrahydrofurfuryl acrylate (THFA). Then, two fillers derived from different industrial wastes, corn (GTF) and wine (WPL-CF) by-products, were added to the AESO-based formulations to develop polymer composites with improved properties. The printability by LCD of the photocurable formulations was widely studied. Bio-based objects with different geometries were realized, showing printing accuracy, layer adhesion, and accurate details. The thermo-mechanical and mechanical properties of the 3D-printed composites were tested by TGA, DMA, and tensile tests. The results revealed that the agro-wastes’ addition led to a remarkable increase in the elastic modulus, tensile strength, and glass transition temperature in the glassy state for the systems containing IBOMA and for flexible structures in the rubbery region for systems containing THFA. AESO-based polymers demonstrated tunable properties, varying from rigid to flexible, in the presence of different diluents and biofillers. This finding paves the way for the use of this kind of composite in applications, such as biomedical for the realization of prostheses.

The surface properties of drug containers should reduce the adsorption of the drug and avoid packaging surface/drug interactions, especially in the case of biologically-derived products. Here, we developed a multi-technique approach that combined Differential Scanning Calorimetry (DSC), Atomic Force Microscopy (AFM), Contact Angle (CA), Quartz Crystal Microbalance with Dissipation monitoring (QCM-D), and X-ray Photoemission Spectroscopy (XPS) to investigate the interactions of rhNGF on different pharma grade polymeric materials. Polypropylene (PP)/polyethylene (PE) copolymers and PP homopolymers, both as spin-coated films and injected molded samples, were evaluated for their degree of crystallinity and adsorption of protein. Our analyses showed that copolymers are characterized by a lower degree of crystallinity and lower roughness compared to PP homopolymers. In line with this, PP/PE copolymers also show higher contact angle values, indicating a lower surface wettability for the rhNGF solution on copolymers than PP homopolymers. Thus, we demonstrated that the chemical composition of the polymeric material and, in turn, its surface roughness determine the interaction with the protein and identified that copolymers may offer an advantage in terms of protein interaction/adsorption. The combined QCM-D and XPS data indicated that protein adsorption is a self-limiting process that passivates the surface after the deposition of roughly one molecular layer, preventing any further protein adsorption in the long term.

The present work investigated the possibility to use wet blue (WB) leather wastes as natural reinforcing fibers within different polymer matrices. After their preparation and characterization, WB fibers were melt-mixed at 10 wt.% with poly(lactic acid) (PLA), polyamide 12 (PA12), thermoplastic elastomer (TPE), and thermoplastic polyurethane (TPU), and the obtained samples were subjected to rheological, thermal, thermo-mechanical, and viscoelastic analyses. In parallel, morphological properties such as fiber distribution and dispersion, fiber–matrix adhesion, and fiber exfoliation phenomena were analyzed through a scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) to evaluate the relationship between the compounding process, mechanical responses, and morphological parameters. The PLA-based composite exhibited the best results since the Young modulus (+18%), tensile strength (+1.5%), impact (+10%), and creep (+5%) resistance were simultaneously enhanced by the addition of WB fibers, which were well dispersed and distributed in and significantly branched and interlocked with the polymer matrix. PA12- and TPU-based formulations showed a positive behavior (around +47% of the Young modulus and +40% of creep resistance) even if the not-optimal fiber–matrix adhesion and/or the poor de-fibration of WB slightly lowered the tensile strength and elongation at break. Finally, the TPE-based sample exhibited the worst performance because of the poor affinity between hydrophilic WB fibers and the hydrophobic polymer matrix.

In recent years, biopolymers have been attracting the attention of researchers and specialists from different fields, including biotechnology, material science, engineering, and medicine. The reason is the possibility of combining sustainability with scientific and technological progress. This is an extremely broad research topic, and a distinction has to be made among different classes and types of biopolymers. Polyhydroxyalkanoate (PHA) is a particular family of polyesters, synthetized by microorganisms under unbalanced growth conditions, making them both bio-based and biodegradable polymers with a thermoplastic behavior. Recently, PHAs were used more intensively in biomedical applications because of their tunable mechanical properties, cytocompatibility, adhesion for cells, and controllable biodegradability. Similarly, the 3D-printing technologies show increasing potential in this particular field of application, due to their advantages in tailor-made design, rapid prototyping, and manufacturing of complex structures. In this review, first, the synthesis and the production of PHAs are described, and different production techniques of medical implants are compared. Then, an overview is given on the most recent and relevant medical applications of PHA for drug delivery, vessel stenting, and tissue engineering. A special focus is reserved for the innovations brought by the introduction of additive manufacturing in this field, as compared to the traditional techniques. All of these advances are expected to have important scientific and commercial applications in the near future.

Invisible orthodontic aligners (IOAs) have been introduced in the orthodontic field as an innovative alternative for fixed brackets, in relation to their ability to be easily inserted/removed from the oral cavity without affecting the chewing ability and the aesthetic of the patients. The paper provides a complete physicochemical and mechanical characterization of thermoplastic materials in the form of disks used for commercial IOAs. A wide palette of specific techniques is considered, from tensile tests and dynamic-mechanical analysis, to X-Ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transformation infrared spectroscopy (FTIR-ATR) analyses and water absorption tests. The disks are investigated before and after immersion into staining beverages (red wine, coffee, nicotine and artificial saliva), in terms of colour variations, transparency, and microscopic surface modifications by means of colorimetry, UV-VIS absorbance and scanning electron microscopy (SEM). Among all the samples, polyurethane (PU) exhibited the highest crystallinity and the highest values of mechanical and thermal resistance, while the poly(ethylene terephthalate)-glycol (PETG) samples presented better transparency and less ability to absorb water. Moreover, red wine and coffee give noticeable colour variations after 14 days of immersion, together with a slight reduction of transparency.

A series of novel Si–O–Si crosslinked organic/inorganic hybrid semi-crystalline polymers with shape memory properties was prepared from alkoxysilane-terminated poly(butylene succinate) (PBS) by water-induced silane crosslinking under organic solvent-free and catalyst-free conditions. The hydrolyzation and condensation of alkoxysilane end groups allowed for the generation of silica-like crosslinking points between the polymeric chains, acting not only as chemical net-points, but also as inorganic filler for a reinforcement effect. The resulting networks were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic-mechanical analysis (DMA) and tensile and shape memory tests to gain insight into the relationship between the polymeric structure, the morphology and the properties. By controlling the molecular weight of the PBS precursor, a fine tuning of the crosslinking density and the inorganic content of the resulting network was possible, leading to different thermal, mechanical and shape memory properties. Thanks to their suitable morphology consisting of crystalline domains, which represent the molecular switches between the temporary and permanent shapes, and chemical net-points, which permit the shape recovery, the synthesized materials showed good shape memory characteristics, being able to fix a significant portion of the applied strain in a temporary shape and to restore their original shape above their melting temperature.

In this paper we used high- and low-resolution solid state Nuclear Magnetic Resonance (NMR) techniques to investigate a series of polyisoprene samples filled with silica generated in situ from tetraethoxysilane by sol-gel process. In particular, 1H spin-lattice and spin-spin relaxation times allowed us to get insights into the dynamic properties of both the polymer bulk and the bound rubber, and to obtain a comparative estimate of the amount of bound rubber in samples prepared with different compositions and sol-gel reaction times. In all samples, three fractions with different mobility could be distinguished by 1H T2 and ascribed to loosely bound rubber, polymer bulk, and free chain ends. The amount of bound rubber was found to be dependent on sample preparation, and it resulted maximum in the sample showing the best dispersion of silica domains in the rubber matrix. The interpretation of the loosely bound rubber in terms of “glassy” behaviour was discussed, also on the basis of 1H T1 and T1ρ data.

The limited availability of materials with special properties represents one of the main limitations to a wider application of polymer-based additive manufacturing technologies. Filled resins are usually not suitable for vat photo-polymerization techniques such as stereolithography (SLA) or digital light processing (DLP) due to a strong increment of viscosity derived from the presence of rigid particles within the reactive suspension. In the present paper, the possibility to in situ generate silver nanoparticles (AgNPs) starting from a homogeneous liquid system containing a well dispersed silver salt, which is subsequently reduced to metallic silver during stereolithographic process, is reported. The simultaneous photo-induced cross-linking of the acrylic resin produces a filled thermoset resin with thermal-mechanical properties significantly enhanced with respect to the unfilled resin, even at very low AgNPs concentrations. With this approach, the use of silver salts having carbon-carbon double bonds, such as silver acrylate and silver methacrylate, allows the formation of a nanocomposite structure in which the release of by-products is minimized due to the active role of all the reactive components in the three dimensional (3D)-printing processes. The synergy, between this nano-technology and the geometrical freedom offered by SLA, could open up a wide spectrum of potential applications for such a material, for example in the field of food packaging and medical and healthcare sectors, considering the well-known antimicrobial effects of silver nanoparticles.

Recovering of significant skeletal defects could be partially abortive due to the perturbations that affect the regenerative process when defects reach a critical size, thus resulting in a non-healed bone. The current standard treatments include allografting, autografting, and other bone implant techniques. However, although they are commonly used in orthopedic surgery, these treatments have some limitations concerning their costs and their side effects such as potential infections or malunions. On this account, the need for suitable constructs to fill the gap in wide fractures is still urgent. As an innovative solution, scleral ossicles (SOs) can be put forward as natural scaffolds for bone repair. SOs are peculiar bony plates forming a ring at the scleral-corneal border of the eyeball of lower vertebrates. In the preliminary phases of the study, these ossicles were structurally and functionally characterized. The morphological characterization was performed by SEM analysis, MicroCT analysis and optical profilometry. Then, UV sterilization was carried out to obtain a clean support, without neither contaminations nor modifications of the bone architecture. Subsequently, the SO biocompatibility was tested in culture with different cell lines, focusing the attention to the differentiation capability of endothelial and osteoblastic cells on the SO surface. The results obtained by the above mentioned analysis strongly suggest that SOs can be used as bio-scaffolds for functionalization processes, useful in regenerative medicine.