Emanuela Calò

Synthesis of a novel cardanol-based benzoxazine monomer and environmentally sustainable production of polymers and bio-composites

A novel pre-polymer deriving from cardanol—a well known renewable organic resource and harmful by-product of the cashew industry—in combination with cellulose based materials (i.e. jute fibres) has been used to produce bio-composites having a high percentage of renewable materials. Cardanol and its derivatives are considered nowadays very attractive precursors to developing new materials from renewable bio-sources to use in eco-friendly processes. This paper deals with the synthesis and characterization of a novel cardanol based benzoxazine monomer used for the preparation of new bio-composites. The new cardanol-based benzoxazine was characterised by 1H and 13C NMR, FT-IR spectroscopies and LC mass spectrometry analysis, while a differential scanning calorimeter was used to study and monitor the polymerization process. Different bio-composites have been obtained by thermal cure of jute fibres impregnated with a cardanol based benzoxazine resin.

An investigation into sintering of PA6 nanocomposite powders for rotational molding

The objective of this work is to study the sintering behavior of polyamide 6 (PA6) powders and PA6 nanocomposites by means of thermomechanical (TMA) and dimensionless analysis in view of its technological application in rotational molding. TMA analysis was used to monitor the bulk density evolution of PA6 powders and PA6 nanocomposites when heated above the melting temperature. Experimental TMA results indicate that the sintering of PA6 and PA6 nanocomposites occurs in two different steps, namely powder coalescence and void removal. Furthermore, TMA analysis showed that relevant degradation phenomena occur during the sintering of PA6 and PA6 nanocomposites, leading to gas formation in the molten polymer. The suitability of these materials in rotational molding was then assessed by defining a processing window, as the temperature difference between the endset sintering and the onset degradation. The heating rate dependence of the processing window was explained by means of dimensionless analysis, showing that powder coalescence is influenced by the viscosity evolution of the matrix, whereas void removal is influenced by the gas diffusivity inside the molten matrix. Therefore, the diffusion activation energy correlates the endset sintering temperature to the heating rate. On the other hand, the onset degradation temperature depends on the heating rate, due to the characteristic activation energy of the degradation process. Accordingly, the width of the processing window mainly depends on the values of the activation energies for diffusivity and degradation. The width of the processing window for neat PA6 was found to be too narrow to candidate this polymer for rotational molding. The addition of nanofiller causes a narrowing of the processing window, whereas the PA6 matrix modified with a thermal stabilizer showed a sufficiently broad processing window, compatible for use in rotational molding.

Assessment of collagen crosslinking and denaturation for the design of regenerative scaffolds

Crosslinking and denaturation were two variables that deeply affected the performance of collagen-based scaffolds designed for tissue regeneration. If crosslinking enhances the mechanical properties and the enzymatic resistance of collagen, while masking or reducing the available cell binding sites, denaturation has very opposite effects, as it impairs the mechanical and the enzymatic stability of collagen, but increases the number of exposed cell adhesive domains. The quantification of both crosslinking and denaturation was thus fundamental to the design of collagen-based scaffolds for selected applications. The aim of this work was to investigate the extents of crosslinking and denaturation of collagen-based films upon dehydrothermal (DHT) treatment, that is, one of the most commonly employed methods for zero-length crosslinking that shows the unique ability to induce partial denaturation. Swelling measurements, differential scanning calorimetry, Fourier transform infrared spectroscopy, colorimetric assays for the quantification of primary amines, and mechanical tests were performed to analyze the effect of the DHT temperature on crosslinking and denaturation. In particular, chemically effective and elastically effective crosslink densities were evaluated. Both crosslinking and denaturation were found to increase with the DHT temperature, although according to different trends. The results also showed that DHT treatments performed at temperatures up to 120°C maintained the extent of denaturation under 25%. Coupling a mild DHT treatment with further crosslinking may thus be very useful not only to modulate the crosslink density, but also to induce a limited amount of denaturation, which shows potential to partially compensate the loss of cell binding sites caused by crosslinking.

Rotational Molding of Polyamide-6 Nanocomposites with Improved Flame Retardancy

Abstract The aim of this work was to develop polyamide-6/ organic-modified montmorillonite (omMMT) nanocomposites for the production of hollow parts by rotational molding. Particular emphasis was placed on the mechanical and flame retardancy properties needed for the fabrication of vessels for flammable liquids. The morphology of the melt compounded nanocomposites, produced by melt compounding, was investigated by X-ray diffraction measurements (WAXD), and Transmission Electron Microscopy (TEM) showed an exfoliated structure. Rheological measurements were used in order to verify whether the viscosity of materials was adequate for rotational molding. While thermomechanical analysis has revealed that neat PA6 and its nanocomposites were not suitable for rotational molding, due to the very low thermal stability of the polymer, the addition of a thermal stabilizer, shifted the onset of degradation to higher temperatures, thus widening the processing window of both PA6 and PA6 nanocomposites. Large-scale vessel prototypes were obtained by rotational molding of thermo-stabilized PA6 and its nanocomposites, and samples extracted from the rotomolded parts were characterized with respect to physical and mechanical properties. It was found that the PA6 nanocomposites exhibited significant improvements at cone calorimeter tests in comparison with neat PA6.

Potential of Electrospun Poly(3-hydroxybutyrate)/Collagen Blends for Tissue Engineering Applications

In this work, tunable nonwoven mats based on poly(3-hydroxybutyrate) (PHB) and type I collagen (Coll) were successfully produced by electrospinning. The PHB/Coll weight ratio (fixed at 100/0, 70/30, and 50/50, resp.) was found to control the morphological, thermal, mechanical, and degradation properties of the mats. Increasing collagen amounts led to larger diameters of the fibers (in the approximate range 600–900 nm), while delaying their thermal decomposition (from 245°C to 262°C). Collagen also accelerated the hydrolytic degradation of the mats upon incubation in aqueous medium at 37°C for 23 days (with final weight losses of 1%, 15%, and 23% for 100/0, 70/30, and 50/50 samples, resp.), as a result of increased mat wettability and reduced PHB crystallinity. Interestingly, 70/30 meshes were the ones displaying the lowest stiffness (~116 MPa; p < 0.05 versus 100/0 and 50/50 meshes), while 50/50 samples had an elastic modulus comparable to that of 100/0 ones (~250 MPa), likely due to enhanced physical crosslinking of the collagen chains, at least at high protein amounts. All substrates were also found to allow for good viability and proliferation of murine fibroblasts, up to 6 days of culture. Collectively, the results evidenced the potential of as-spun PHB/Coll meshes for tissue engineering applications.