Cellulose nanofibers were obtained from microcrystalline cellulose (MCC) by the action of hydrodynamic forces associated with ultrasound. Nanofibers isolated from MCC by applying different ultrasonication conditions were characterized to elucidate their morpho-structural features by field emission scanning electron microscopy, atomic force microscopy, X-ray diffraction, and dynamic light scattering. Several differences were observed regarding the size of the nanofibers obtained in different ultrasonic conditions, but no significant changes in the crystalline structure of cellulose nanofibers were detected. The obtained cellulose fibers were used at low levels (1 to 5 wt.%) as reinforcements in a poly(vinyl alcohol) (PVA) matrix. The mechanical and thermal properties of the PVA/cellulose fibers nanocomposites films were determined. The tensile strength and modulus of the PVA film were significantly improved by the addition of cellulose nanofibers. Slightly higher onset degradation temperatures were obtained for PVA composites in comparison to neat PVA, showing an increase of the thermal stability caused by the addition of cellulose fibers.
3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.
We focused on preparing cellulose nanofibrils by purification, separation, and mechanical treatment of Kombucha membranes (KM) resulted as secondary product from beverage production by fermentation of tea broth with symbiotic culture of bacteria and yeast (SCOBY). We purified KM using two alkaline solutions, 1 and 4 M NaOH, which afterwards were subjected to various mechanical treatments. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light scattering (DLS), X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) were employed to evaluate the purification degree, the size and aspect of cellulose fibrils after each treatment step, the physical-chemical properties of intermediary and final product, and for comparison with micro-crystalline cellulose from wooden sources. We determined that 1 M NaOH solution leads to approx. 85% purification, while a higher concentration assures almost 97% impurities removal. XRD analysis evidenced an increase in crystallinity from 37% to 87% after purification, the characteristic diffractograms of Iα and Iβ cellulose allomorphs, and a further decrease in crystallinity to 46% after microfluidization, fact correlated with a drastically decrease in fibrils’ size. FTIR analysis evidenced the appearance of new chain ends by specific transmission bands at 2941 and 2843cm−1.
Biodegradable blends and nanocomposites were produced from polylactic acid (PLA), poly(3-hydroxybutyrate) (PHB) and cellulose nanocrystals (NC) by a single step reactive blending process using dicumyl peroxide (DCP) as a cross-linking agent. With the aim of gaining more insight into the impact of processing methods upon the morphological, thermal and mechanical properties of these nanocomposites, three different processing techniques were employed: compression molding, extrusion, and 3D printing. The addition of DCP improved interfacial adhesion and the dispersion of NC in nanocomposites as observed by scanning electron microscopy and atomic force microscopy. The carbonyl index calculated from Fourier transform infrared spectroscopy showed increased crystallinity after DCP addition in PLA/PHB and PLA/PHB/NC, also confirmed by differential scanning calorimetry analyses. NC and DCP showed nucleating activity and favored the crystallization of PLA, increasing its crystallinity from 16% in PLA/PHB to 38% in DCP crosslinked blend and to 43% in crosslinked PLA/PHB/NC nanocomposite. The addition of DCP also influenced the melting-recrystallization processes due to the generation of lower molecular weight products with increased mobility. The thermo-mechanical characterization of uncross-linked and cross-linked PLA/PHB blends and nanocomposites showed the influence of the processing technique. Higher storage modulus values were obtained for filaments obtained by extrusion and 3D printed meshes compared to compression molded films. Similarly, the thermogravimetric analysis showed an increase of the onset degradation temperature, even with more than 10 °C for PLA/PHB blends and nanocomposites after extrusion and 3D-printing, compared with compression molding. This study shows that PLA/PHB products with enhanced interfacial adhesion, improved thermal stability, and mechanical properties can be obtained by the right choice of the processing method and conditions using NC and DCP for balancing the properties.