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

Influence of Thermal Treatment on Mechanical and Morphological Characteristics of Polyamide 11/Cellulose Nanofiber Nanocomposites

Nanocomposite films were prepared from polyamide 11 (PA11) and cellulose nanofibers (CN) by melt compounding and compression molding. The impact of thermal treatment on the morphology and mechanical behavior of PA11 and nanocomposite films was studied using dynamic mechanical analysis, tensile tests, X-ray diffraction (XRD), and peak force (PF) QNM technique. Slightly higher storage modulus values were obtained for nanocomposites compared to the matrix before the treatment, but a noticeable increase was observed after the treatment. Although CN addition determined increased tensile strength and modulus both before and after the treatment, the increase was much more significant in the case of treated films. The best mechanical properties were shown by treated PA11 films containing 5 wt% CN, with 40% higher Young’s modulus and with 35% higher tensile strength compared to the matrix. Some of the changes pointed out by static and dynamic mechanical tests were explained by the morphological changes determined by the thermal treatment and emphasized by PF QNM and by the increase of XRD crystallinity. A transition from lamellar stack morphology to one involving spherulites was highlighted by AFM. Thermal treatment has proved a valuable method for improving the mechanical properties of PA11/CN composites

Poly(3-hydroxybutyrate) Nanocomposites with Cellulose Nanocrystals

Poly(3-hydroxybutyrate) (PHB) is one of the most promising substitutes for the petroleum-based polymers used in the packaging and biomedical fields due to its biodegradability, biocompatibility, good stiffness, and strength, along with its good gas-barrier properties. One route to overcome some of the PHB’s weaknesses, such as its slow crystallization, brittleness, modest thermal stability, and low melt strength is the addition of cellulose nanocrystals (CNCs) and the production of PHB/CNCs nanocomposites. Choosing the adequate processing technology for the fabrication of the PHB/CNCs nanocomposites and a suitable surface treatment for the CNCs are key factors in obtaining a good interfacial adhesion, superior thermal stability, and mechanical performances for the resulting nanocomposites. The information provided in this review related to the preparation routes, thermal, mechanical, and barrier properties of the PHB/CNCs nanocomposites may represent a starting point in finding new strategies to reduce the manufacturing costs or to design better technological solutions for the production of these materials at industrial scale. It is outlined in this review that the use of low-value biomass resources in the obtaining of both PHB and CNCs might be a safe track for a circular and bio-based economy. Undoubtedly, the PHB/CNCs nanocomposites will be an important part of a greener future in terms of successful replacement of the conventional plastic materials in many engineering and biomedical applications

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

Poly(lactic acid)/Poly(3-hydroxybutyrate) Biocomposites with Differently Treated Cellulose Fibers

The growing concern about environmental pollution has generated an increased demand for biobased and biodegradable materials intended particularly for the packaging sector. Thus, this study focuses on the effect of two different cellulosic reinforcements and plasticized poly(3-hydroxybutyrate) (PHB) on the properties of poly(lactic acid) (PLA). The cellulose fibers containing lignin (CFw) were isolated from wood waste by mechanical treatment, while the ones without lignin (CF) were obtained from pure cellulose by acid hydrolysis. The biocomposites were prepared by means of a melt compounding-masterbatch technique for the better dispersion of additives. The effect of the presence or absence of lignin and of the size of the cellulosic fibers on the properties of PLA and PLA/PHB was emphasized by using in situ X-ray diffraction, polarized optical microscopy, atomic force microscopy, and mechanical and thermal analyses. An improvement of the mechanical properties of PLA and PLA/PHB was achieved in the presence of CF fibers due to their smaller size, while CFw fibers promoted an increased thermal stability of PLA/PHB, owing to the presence of lignin. The overall thermal and mechanical results show the great potential of using cheap cellulose fibers from wood waste to obtain PLA/PHB-based materials for packaging applications as an alternative to using fossil based materials. In addition, in situ X-ray diffraction analysis over a large temperature range has proven to be a useful technique to better understand changes in the crystal structure of complex biomaterials

Complex Effects of Hemp Fibers and Impact Modifiers in Multiphase Polypropylene Systems

Natural fibers-reinforced polymer composites have progressed rapidly due to their undeniable advantages. Most of the commercial polypropylene (PP)-based materials are characterized by either high impact toughness or high stiffness, while the manufacture of PP composites with both good toughness and stiffness is challenging at present. In this work, poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) and poly(styrene-b-butadiene-b-styrene) (SBS) copolymers were used in different amounts as modifiers in PP/hemp fibers (HF) composites, with the aim to use them for electrical vehicle parts. The interface in these multiphase systems was controlled by the addition of maleated polypropylene (MAPP). SEBS and SBS showed different effects on the elongation at break of the blends and the corresponding composites due to the HF that stiffened the multiphase systems. Similarly, a different action of MAPP was observed in the composites containing SEBS or SBS: higher Young’s and storage moduli were obtained for the composite containing SBS, while greater elongation at break and impact strength values were recorded for the SEBS-containing system. In addition, a remarkable dispersion in the MAPP-containing composite and two times smaller average particle size were revealed by the SEM analysis for the SEBS particles compared to the SBS ones. The higher affinity of SEBS for PP compared to that for SBS and the different morphological characteristics of the systems containing SEBS and SBS may explain the different effects of these impact modifiers on the mechanical properties of the composites. The composites developed in this work were designed as substitutes for the fully synthetic polymeric materials or metal components used in the manufacturing of automotive parts

PREPARATION AND CHARACTERIZATION OF PVA COMPOSITES WITH CELLULOSE NANOFIBERS OBTAINED BY ULTRASONICATION

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

Treatment of Nanocellulose by Submerged Liquid Plasma for Surface Functionalization

Tailoring the surface properties of nanocellulose to improve the compatibility of components in polymer nanocomposites is of great interest. In this work, dispersions of nanocellulose in water and acetonitrile were functionalized by submerged plasmas, with the aim of increasing the quality of this reinforcing agent in biopolymer composite materials. Both the morphology and surface chemistry of nanocellulose were influenced by the application of a plasma torch and filamentary jet plasma in a liquid suspension of nanocellulose. Depending on the type of plasma source and gas mixture the surface chemistry was modified by the incorporation of oxygen and nitrogen containing functional groups. The treatment conditions which lead to nanocellulose based polymer nanocomposites with superior mechanical properties were identified. This work provides a new eco-friendly method for the surface functionalization of nanocellulose directly in water suspension, thus overcoming the disadvantages of chemical treatments