Chemical-free Reactive Melt Processing of Biosourced Poly(butylene-succinate-adipate) for Improved Mechanical Properties and Recyclability.

Biosourced and biodegradable polyesters like poly(butylene succinate-co-butylene adipate) (PBSA) are gaining traction as promising alternatives to oil-based thermoplastics for single-use applications. However, the mechanical and rheological properties of PBSA are affected by its thermomechanical sensitivity during its melt processing, also hindering PBSA mechanical recycling. Traditional reactive melt processing (RP) methods use chemical additives to counteract these drawbacks, compromising sustainability. This study proposes a green reactive method during melt compounding for PBSA based on a comprehensive understanding of its thermomechanical degradative behavior. Under the hypothesis that controlled degradative paths during melt processing can promote branching/recombination reactions without the addition of chemical additives, we aim to enhance PBSA rheological and mechanical performance. An in-depth investigation of the in-line rheological behavior of PBSA was conducted using an internal batch mixer, exploring parameters such as temperature, screw rotation speed, and residence time. Their influence on PBSA chain scissions, branching/recombination, and cross-linking reactions were evaluated to identify optimal conditions for effective RP. Results demonstrate that specific processing conditions, for example, twelve minutes processing time, 200 °C temperature, and 60 rpm screw rotation speed, promote the formation of the long chain branched structure in PBSA. These structural changes resulted in a notable enhancement of the reacted PBSA rheological and mechanical properties, exhibiting a 23% increase in elastic modulus, a 50% increase in yield strength, and an 80% increase in tensile strength. The RP strategy also improved PBSA mechanical recycling, thus making it a potential replacement for low-density polyethylene (LDPE). Ultimately, this study showcases how finely controlling the thermomechanical degradation during reactive melt processing can improve the material's properties, enabling reliable mechanical recycling, which can serve as a green approach for other biodegradable polymers.

Green Composites Based on Hedysarum coronarium with Outstanding FDM Printability and Mechanical Performance.

The addition of natural scraps to biodegradable polymers has gained particular interest in recent years, allowing reducing environmental pollution related to traditional plastic. In this work, new composites were fabricated by adding 10% or 20% of Hedysarum coronarium (HC) flour to Poly (lactic acid) (PLA). The two formulations were first produced by twin screw extrusion and the obtained filaments were then employed for the fabrication of composites, either for compression molding (CM) or by fused deposition modeling (FDM), and characterized from a morphological and mechanical point of view. Through FDM it was possible to achieve dense structures with good wettability of the filler that, on the contrary, cannot be obtained by CM. The results indicate that the filler effectively acts as reinforcement, especially for FDM composites. The most remarkable enhancement was found in the flexural properties (+100% of modulus and ultimate strength), followed by tensile resistance and stiffness (+60%) and impact strength (+50%), whereas a moderate loss in tensile deformability was observed, especially at the highest loading. By adding HC to the polymeric matrix, it was possible to obtain a green, high-performance, and cost-effective composite, which could find applications for the fabrication of panels for furniture or the automotive industry.

Hierarchically Structured Hybrid Membranes for Continuous Wastewater Treatment via the Integration of Adsorption and Membrane Ultrafiltration Mechanisms.

Growing environmental concerns are stimulating researchers to develop more and more efficient materials for environmental remediation. Among them, polymer-based hierarchical structures, attained by properly combining certain starting components and processing techniques, represent an emerging trend in materials science and technology. In this work, graphene oxide (GO) and/or carbon nanotubes (CNTs) were integrated at different loading levels into poly (vinyl fluoride-co-hexafluoropropylene) (PVDF-co-HFP) and then electrospun to construct mats capable of treating water that is contaminated by methylene blue (MB). The materials, fully characterized from a morphological, physicochemical, and mechanical point of view, were proved to serve as membranes for vacuum-assisted dead-end membrane processes, relying on the synergy of two mechanisms, namely, pore sieving and adsorption. In particular, the nanocomposites containing 2 wt % of GO and CNTs gave the best performance, showing high flux (800 L × m-2 h-1) and excellent rejection (99%) and flux recovery ratios (93.3%), along with antifouling properties (irreversible and reversible fouling below 6% and 25%, respectively), and reusability. These outstanding outcomes were ascribed to the particular microstructure employed, which endowed polymeric membranes with high roughness, wettability, and mechanical robustness, these capabilities being imparted by the peculiar self-assembled network of GO and CNTs.

An Overview of Functionalized Graphene Nanomaterials for Advanced Applications.

Interest in the development of graphene-based materials for advanced applications is growing, because of the unique features of such nanomaterials and, above all, of their outstanding versatility, which enables several functionalization pathways that lead to materials with extremely tunable properties and architectures. This review is focused on the careful examination of relationships between synthetic approaches currently used to derivatize graphene, main properties achieved, and target applications proposed. Use of functionalized graphene nanomaterials in six engineering areas (materials with enhanced mechanical and thermal performance, energy, sensors, biomedical, water treatment, and catalysis) was critically reviewed, pointing out the latest advances and potential challenges associated with the application of such materials, with a major focus on the effect that the physicochemical features imparted by functionalization routes exert on the achievement of ultimate properties capable of satisfying or even improving the current demand in each field. Finally, current limitations in terms of basic scientific knowledge and nanotechnology were highlighted, along with the potential future directions towards the full exploitation of such fascinating nanomaterials.

Green Composites Based on PLA and Agricultural or Marine Waste Prepared by FDM.

Three dimensional-printability of green composites is recently growing in importance and interest, especially in the view of feasibility to valorize agricultural and marine waste to attain green fillers capable of reducing bioplastic costs, without compromising their processability and performance from an environmental and mechanical standpoint. In this work, two lignocellulosic fillers, obtained from Opuntia ficus indica and Posidonia oceanica, were added to PLA and processed by FDM. Among the 3D printed biocomposites investigated, slight differences could be found in terms of PLA molecular weight and filler aspect ratio. It was shown that it is possible to replace up to 20% of bioplastic with low cost and ecofriendly natural fillers, without significantly modifying the processability and the mechanical performance of the neat matrix; at the same time, an increase of surface hydrophilicity was found, with possible positive influence on the biodegradability of such materials after disposal.

Flexible mats as promising antimicrobial systems via integration of Thymus capitatus (L.) essential oil into PLA.

Aim: To develop electrospun mats loaded with Thymus capitatus (L.) essential oil (ThymEO) and to study their morpho-mechanical and antimicrobial properties. Materials & methods: Poly(lactic acid) (PLA) mats containing ThymEO were prepared by electrospinning. The effect of ThymEO on the morpho-mechanical properties of fibers was assayed by scanning electron microscopy and dynamometer measurements. The antimicrobial activity of ThymEO delivered either in liquid or vapor phase was assessed through killing curves and invert Petri dishes method. The cytotoxicity was also investigated. Results: The mechanical properties were enhanced by integrating ThymEO into PLA. Both liquid and vapors of ThymEO released from mats caused reductions of microbial viable cells. Negligible cytotoxicity was demonstrated. Conclusion: PLA/ThymEO delivery systems could be suitable for treating microbial infections.

The Effects of Nanoclay on the Mechanical Properties, Carvacrol Release and Degradation of a PLA/PBAT Blend.

The formulation of polymeric films endowed with the abilities of controlled release of antimicrobials and biodegradability is the latest trend of food packaging. Biodegradable polymer (Bio-Flex®)-based nanocomposites containing carvacrol as an antimicrobial agent, and a nanoclay as a filler, were processed into blown films. The presence of such hybrid loading, while not affecting the overall filmability of the neat matrix, led to enhanced mechanical properties, with relative increments up to +70% and +200% in terms of elastic modulus and elongation at break. FTIR/ATR analysis and release tests pointed out that the presence of nanoclay allowed higher carvacrol loading efficiency, reasonably hindering its volatilization during processing. Furthermore, it also mitigated the burst delivery, thereby enabling a more controlled release of the antimicrobial agent. The results of mass loss tests indicated that all the formulations showed a rather fast degradation with mass losses ranging from 37.5% to 57.5% after 876 h. The presence of clay and carvacrol accelerated the mass loss rate of Bio-Flex®, especially when added simultaneously, thus indicating an increased biodegradability. Such ternary systems could be, therefore, particularly suitable as green materials for food packaging applications, and for antimicrobial wrapping applications.

Poly(lactic acid)/carvacrol-based materials: preparation, physicochemical properties, and antimicrobial activity.

The current demand for new antimicrobial systems has stimulated research for the development of poly(lactic acid)/carvacrol (PLA/CAR)-based materials able to hinder the growth and spread of microorganisms. The eco-friendly characteristics of PLA and cytocompatibility make it very promising in the perspective of green chemistry applications as material for food and biomedical employments. The broad-spectrum biological and pharmacological properties of CAR, including antimicrobial activity, make it an interesting bioactive molecule that can be easily compounded with PLA by adopting the same techniques as those commonly used for PLA manufacturing. This review critically discusses the most common methods to incorporate CAR into a PLA matrix and their interference on the morphomechanical properties, release behavior, and antimicrobial activity of systems. The high potential of PLA/CAR materials in terms of chemical-physical and antimicrobial properties can be exploited for the future development of food packaging, coated medical devices, or drug delivery systems.

Influence of Oxidation Level of Graphene Oxide on the Mechanical Performance and Photo-Oxidation Resistance of a Polyamide 6.

The aim of this work is to study the relationship between the chemical-physical properties of graphene oxide (GO) and the performance of a polyamide 6 (PA6) in terms of mechanical reinforcement and resistance to UV-exposure. For this purpose, two samples of GO possessing different oxidation degrees were added (0.75 wt.%) to PA6 by way of a two-step technique and the materials achieved were carefully analysed from a morphological, chemical-physical, mechanical point of view. Photo-oxidation tests were carried out to assess the performance of this class of nanohybrids after 240 h of UV-exposure. The results reveal that both nanocomposites exhibit enhanced mechanical performance and durability of PA6. However, the most oxidized GO led to a higher increase of mechanical properties and a stronger resistance to UV-exposure. All the analyses confirm that both GO samples are well dispersed and covalently attached to PA6. However, the higher the oxidation level of GO the stronger and the more extended the chemical interphase of the nanocomposite. As regards photochemical stability, both GO samples display UV-shielding capacity but the most oxidized GO also shows radical scavenging activity by virtue of its nanocavities and defects, imparted by prolonged oxidation, which endows PA6 with an outstanding durability even after 240 h of UV-exposure.

Degradation and Recycling of Films Based on Biodegradable Polymers: A Short Review.

The environmental performance of biodegradable materials has attracted attention from the academic and the industrial research over the recent years. Currently, degradation behavior and possible recyclability features, as well as actual recycling paths of such systems, are crucial to give them both durability and eco-sustainability. This paper presents a review of the degradation behaviour of biodegradable polymers and related composites, with particular concern for multi-layer films. The processing of biodegradable polymeric films and the manufacturing and properties of multilayer films based on biodegradable polymers will be discussed. The results and data collected show that: poly-lactic acid (PLA), poly-butylene adipate-co-terephthalate (PBAT) and poly-caprolactone (PCL) are the most used biodegradable polymers, but are prone to hydrolytic degradation during processing; environmental degradation is favored by enzymes, and can take place within weeks, while in water it can take from months to years; thermal degradation during recycling basically follows a hydrolytic path, due to moisture and high temperatures (ß-scissions and transesterification) which may compromise processing and recycling; ultraviolet (UV) and thermal stabilization can be adequately performed using suitable stabilizers.

Nanocarbons in Electrospun Polymeric Nanomats for Tissue Engineering: A Review.

Electrospinning is a versatile process technology, exploited for the production of fibers with varying diameters, ranging from nano- to micro-scale, particularly useful for a wide range of applications. Among these, tissue engineering is particularly relevant to this technology since electrospun fibers offer topological structure features similar to the native extracellular matrix, thus providing an excellent environment for the growth of cells and tissues. Recently, nanocarbons have been emerging as promising fillers for biopolymeric nanofibrous scaffolds. In fact, they offer interesting physicochemical properties due to their small size, large surface area, high electrical conductivity and ability to interface/interact with the cells/tissues. Nevertheless, their biocompatibility is currently under debate and strictly correlated to their surface characteristics, in terms of chemical composition, hydrophilicity and roughness. Among the several nanofibrous scaffolds prepared by electrospinning, biopolymer/nanocarbons systems exhibit huge potential applications, since they combine the features of the matrix with those determined by the nanocarbons, such as conductivity and improved bioactivity. Furthermore, combining nanocarbons and electrospinning allows designing structures with engineered patterns at both nano- and microscale level. This article presents a comprehensive review of various types of electrospun polymer-nanocarbon currently used for tissue engineering applications. Furthermore, the differences among graphene, carbon nanotubes, nanodiamonds and fullerenes and their effect on the ultimate properties of the polymer-based nanofibrous scaffolds is elucidated and critically reviewed.

Development of polymeric functionally graded scaffolds: a brief review.

Over recent years, there has been a growing interest in multilayer scaffolds fabrication approaches. In fact, functionally graded scaffolds (FGSs) provide biological and mechanical functions potentially similar to those of native tissues. Based on the final application of the scaffold, there are different properties (physical, mechanical, biochemical, etc.) which need to gradually change in space. Therefore, a number of different technologies have been investigated, and often combined, to customize each region of the scaffolds as much as possible, aiming at achieving the best regenerative performance.In general, FGSs can be categorized as bilayered or multilayered, depending on the number of layers in the whole structure. In other cases, scaffolds are characterized by a continuous gradient of 1 or more specific properties that cannot be related to the presence of clearly distinguished layers. Since each traditional approach presents peculiar advantages and disadvantages, FGSs are good candidates to overcome the limitations of current treatment options. In contrast to the reviews reported in the literature, which usually focus on the application of FGS, this brief review provides an overview of the most common strategies adopted to prepare FGS.

A Facile and Eco-friendly Route to Fabricate Poly(Lactic Acid) Scaffolds with Graded Pore Size.

Over the recent years, functionally graded scaffolds (FGS) gaineda crucial role for manufacturing of devices for tissue engineering. The importance of this new field of biomaterials research is due to the necessity to develop implants capable of mimicking the complex functionality of the various tissues, including a continuous change from one structure or composition to another. In this latter context, one topic of main interest concerns the design of appropriate scaffolds for bone-cartilage interface tissue. In this study, three-layered scaffolds with graded pore size were achieved by melt mixing poly(lactic acid) (PLA), sodium chloride (NaCl) and polyethylene glycol (PEG). Pore size distributions were controlled by NaCl granulometry and PEG solvation. Scaffolds were characterized from a morphological and mechanical point of view. A correlation between the preparation method, the pore architecture and compressive mechanical behavior was found. The interface adhesion strength was quantitatively evaluated by using a custom-designed interfacial strength test. Furthermore, in order to imitate the human physiology, mechanical tests were also performed in phosphate buffered saline (PBS) solution at 37 °C. The method herein presented provides a high control of porosity, pore size distribution and mechanical performance, thus offering the possibility to fabricate three-layered scaffolds with tailored properties by following a simple and eco-friendly route.

Incorporation of an antibiotic in poly(lactic acid) and polypropylene by melt processing.

PURPOSE: In this work an antibiotic, ciprofloxacin (CFX), was incorporated into 2 different polymeric matrices, poly(lactic acid) (PLA) and polypropylene (PP), to provide them with antimicrobial properties. The influence of CFX content on release kinetics and on antimicrobial and mechanical properties was evaluated. METHODS: CFX was incorporated into both the polymers by melt mixing. RESULTS: The effect of CFX incorporation was found to strongly depend on which polymer matrix was used. In particular, the antimicrobial tests revealed that PLA samples containing CFX produced no inhibition zone and only a slight antibacterial activity was observed when the highest concentration of CFX was added to PLA. On the contrary, PP-based materials incorporating CFX, even those containing the smallest concentration of antibiotic, showed antimicrobial activity. These results were found to be in good agreement with the evaluation of the CFX release. CONCLUSIONS: The negative findings of PLA-based systems are attributed to degradation phenomena that occur during the melt processing, involving some interaction between PLA and CFX. A proposed reaction mechanism between CFX and PLA occurring in the melt is presented.

Effect of Graphene Nanoplatelets on the Physical and Antimicrobial Properties of Biopolymer-Based Nanocomposites.

In this work, biopolymer-based nanocomposites with antimicrobial properties were prepared via melt-compounding. In particular, graphene nanoplatelets (GnPs) as fillers and an antibiotic, i.e., ciprofloxacin (CFX), as biocide were incorporated in a commercial biodegradable polymer blend of poly(lactic acid) (PLA) and a copolyester (BioFlex®). The prepared materials were characterized by scanning electron microscopy (SEM), and rheological and mechanical measurements. Moreover, the effect of GnPs on the antimicrobial properties and release kinetics of CFX was evaluated. The results indicated that the incorporation of GnPs increased the stiffness of the biopolymeric matrix and allowed for the tuning of the release of CFX without hindering the antimicrobial activity of the obtained materials.