The Use of Graphene and Its Derivatives for the Development of Polymer Matrix Composites by Stereolithographic 3D Printing

Significant advances in graphene-based materials have facilitated the development of various composites structures in a diverse range of industry sectors. At present, the preparation of graphene-added materials is mainly developed through traditional methods. However, in recent years, additive manufacturing emerged as a promising approach that enables the printing of complex objects in a layer-by-layer fashion, without the need for moulds or machining equipment. This paper reviews the most recent reports on graphene-based photopolymerizable resins developed for stereolithography (SLA), with particular consideration for medical applications. The characteristics of the SLA technology, the most suitable raw materials and formulations and the properties of final 3D products are described. Throughout, a specific focus is placed on the mechanical properties and biocompatibility of the final 3D-printed object. Finally, remaining challenges and future directions are also discussed

Editorial on Special Issue “Biomaterials, Polymers and Tissue Engineering”

The development of new materials, new manufacturing methods, and new techniques has attracted interest from many researchers in recent decades [...

Recent Advances in 3D Printing of Aliphatic Polyesters

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

Biocomposites from Polylactic Acid and Bacterial Cellulose Nanofibers Obtained by Mechanical Treatment

Bacterial cellulose nanofibers (BCNF), obtained by the mechanical disintegration of BC pellicles, were used without any surface treatment for the fabrication of poly(lactic acid) (PLA) nanocomposites by a melt compounding process. The addition of BCNF in different amounts improved both the Young’s modulus and tensile strength of PLA. A 22% increase in these properties was observed in the nanocomposite with 2 wt.% nanofibers, due to the BCNF network formed at this concentration and characterized by atomic force microscopy. BCNF addition also increased the crystallinity and thermal stability of PLA, which were evaluated by thermal analysis. Due to the high purity of BCNF and the environmental friendliness of melt processing, it was concluded that PLA/BCNF nanocomposites can be designed for biomedical field and food packaging

Morpho-Structural, Thermal and Mechanical Properties of PLA/PHB/Cellulose Biodegradable Nanocomposites Obtained by Compression Molding, Extrusion, and 3D Printing

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

Sponges from Plasma Treated Cellulose Nanofibers Grafted with Poly(ethylene glycol)methyl Ether Methacrylate

In this work, cellulose nanofibers (CNF) were surface treated by plasma and grafted with poly(ethylene glycol)methyl ether methacrylate (PEGMMA) for increasing mechanical strength and hydrophobicity. The surface characteristics of the sponges were studied by scanning electron microscopy, micro-computed tomography, and Fourier transform infrared spectroscopy, which demonstrated successful surface modification. Plasma treatment applied to CNF suspension led to advanced defibrillation, and the resulting sponges (CNFpl) exhibited smaller wall thickness than CNF. The grafting of PEGMMA led to an increase in the wall thickness of the sponges and the number of larger pores when compared with the non-grafted counterparts. Sponges with increased hydrophobicity demonstrated by an almost 4 times increase in the water contact angle and better mechanical strength proved by 2.5 times increase in specific compression strength were obtained after PEGMMA grafting of plasma treated CNF. Cells cultivated on both neat and PEGMMA-grafted CNF sponges showed high viability (>99%). Remarkably, CNF grafted with PEGMMA showed better cell viability as compared with the untreated CNF sample; this difference is statistically significant (p < 0.05). In addition, the obtained sponges do not trigger an inflammatory response in macrophages, with TNF-α secretion by cells in contact with CNFpl, CNF-PEGMMA, and CNFpl-PEGMMA samples being lower than that observed for the CNF sample. All these results support the great potential of cellulose nanofibers surface treated by plasma and grafted with PEGMMA for biomedical applications

Surface Treatment of Bacterial Cellulose in Mild, Eco-Friendly Conditions

Bacterial cellulose (BC) with increased hydrophobicity is required for several applications including packaging. Surface functionalization of BC may provide good resistance to moisture, increased barrier properties or improved compatibility to polymer matrices. For this purpose, chemical grafting of BC in mild, eco-friendly conditions was carried out using different agents. BC membranes were surface functionalized with vinyl-triethoxy silane (VS) or 3-aminopropyl triethoxysilane (APS), by acylation and acrylation. The efficiency of the surface treatments was highlighted by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, by contact angle measurements and by dynamic mechanical analysis. The morphological investigation by atomic force microscopy and scanning electron microscopy revealed an increased compactness for surface functionalized BC, which correlated well with the different increase of the contact angle. BC treated with APS and VS showed more than a twofold increase in contact angle value. Similarly, the crystallinity degree was reduced to 69.6% and 72.9% after APS and VS treatments as compared with 84.1% for untreated BC, confirming the grafting reaction and the decrease in hydrogen bonding. All the applied treatments delayed the degradation of BC. However, the highest increase in thermal stability was observed for silanes treated membranes. Effective, eco-friendly methods for improving the surface hydrophobicity of bacterial cellulose for food packaging were proposed in this study