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

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

Ag⁰–Ginger Nanocomposites Integrated into Natural Hydrogelated Matrices Used as Antimicrobial Delivery Systems Deposited on Cellulose Fabrics

In the textile, medical, and food industries, many of the applications have targeted the use of textile fabrics with antimicrobial properties. Obtaining eco-friendly coatings is of wide interest, especially for applications related to wound dressing or to food packaging. In order to obtain coatings with antimicrobial properties through environmentally friendly methods, a series of experiments were carried out on the use of natural polymers loaded with silver nanoparticles. In this study, coatings with antimicrobial properties were obtained by depositing natural composites based on rice flour, carob flour, or alginate on cotton fabrics. These antimicrobial coatings were multicomponent systems, in which the host matrix was generated via hydration of natural polymers. The nanocomposite obtained from the phytosynthesis of silver particles in ginger extract was embedded in hydrogel matrices. The multicomponent gels obtained by embedding silver nanoparticles in natural polymer matrices were deposited on cotton fabric and were studied in relation to nanoparticles and the type of host matrix, and the antimicrobial activity was evaluated. Fabrics coated with such systems provide a hydrophilic surface with antimicrobial properties and can therefore be used in various areas where textiles provide antibacterial protection

Opposite Roles of Bacterial Cellulose Nanofibers and Foaming Agent in Polyhydroxyalkanoate-Based Materials

In this work, an economically feasible procedure was employed to produce poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)-based foams. Thermally expandable microspheres (TESs) were used as a blowing agent, while bacterial cellulose (BC) nanofibers served both as a reinforcing agent and as a means of improving biocompatibility. PHBV was plasticized with acetyltributylcitrate to reduce the processing temperature and ensure the maximum efficiency of the TES agent. The morphological investigation results for plasticized PHBV foams showed well-organized porous structures characterized by a porosity of 65% and the presence of both large pores (>100 µm) and finer ones, with a higher proportion of pores larger than 100 µm being observed in the PHBV nanocomposite containing TESs and BC. The foamed structure allowed an increase in the water absorption capacity of up to 650% as compared to the unfoamed samples. TESs and BC had opposite effects on the thermal stability of the plasticized PHBV, with TESs decreasing the degradation temperature by about 17 °C and BC raising it by 3–4 °C. A similar effect was observed for the melting temperature. Regarding the mechanical properties, the TESs had a flexibilizing effect on plasticized PHBV, while BC nanofibers showed a stiffening effect. An in vitro cytotoxicity test showed that all PHBV compounds exhibited high cell viability. The addition of TESs and BC nanofibers to PHBV biocomposites enabled balanced properties, along with lower costs, making PHBV a more attractive biomaterial for engineering, packaging, or medical device applications