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 comm…

Functionalization of Graphene with Molecules and/or Nanoparticles for Advanced Applications

Graphene is considered the material of the third millennium, due to its extraordinary electronic and mechanical properties, and due to the possibility to modulate its conductivity, flexibility, elasticity, transparency, and biocompatibility by bottom-up approach. The possibility to gather the proper- ties of graphene and graphene oxide with those of functional moieties or nanoparticles is herein reviewed. The synthetic approaches proposed, either covalent or noncovalent, are aimed to tune appropriately graphene’s properties for the realization of materials for advanced uses, such as bio- medical applications, sensors, catalysis, and energy devices. In particular, methods based on covalent l…

Wet electrospinning-aided self-assembly of multifunctional GO-CNT@PCL core-shell nanocomposites with spider leg bioinspired hierarchical architectures

We report a fast route enabling the multiscale design of nanohybrid structures comprising a 3D fibrous network of polycaprolactone (PCL) wrapped by graphene oxide (GO) sheets onto which carbon nanotube (CNT) brushes are anchored. The method relies on electrospinning PCL solutions onto a suspension of GO and CNTs in ethanol. Self-assembly is due to electrostatic wrapping of GO sheets around PCL fibers and 7C-7C stacking between GO and CNTs. Hierarchical architecture and nanopatterned surface allow gathering the starting properties of PCL, GO and CNTs into lightweight (99% porosity) yet robust (1575% stiffness improvement), amphiphilic monoliths that can remove methylene blue and/or methyl or…

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 t…

Rapid One-Step Fabrication of Graphene Oxide-Decorated Polycaprolactone Three-Dimensional Templates for Water Treatment

Coating of flexible substrates is crucial to prepare versatile, multifunctional materials. However, exploration of effective fabrication approaches is still a challenging issue, because the pathways generally proposed require time-consuming, multistep protocols. Here, we developed a one-pot process for decorating either pearl necklace-like or fibrous fluffy-like structures of polycaprolactone (PCL) with graphene oxide (GO) skin. PCL solutions were dry jet-wet electrosprayed or electrospun into a stirred liquid collector constituted by ethanol-containing GO nanoparticles. The stirred liquid collector enables the formation of 3D-structures, whose microarchitecture can be designed by controlli…

ECOCOMPOSITI MATER-BI®/FARINA DI LEGNO: OTTIMIZZAZIONE DELLE PROPRIETA’ ATTRAVERSO ANALISI STATISTICA E BIODEGRADAZIONE

Enhancing the mechanical performance of polymer based nanocomposites by plasma-modification of nanoparticles

Abstract The possibility of enhancing the mechanical performance of two different polymer-based nanocomposites using polyamide 6 (PA6) and poly[ethylene-co-(vinyl acetate)] (EVA) as matrices was investigated. The nanofillers used were, respectively, either carbon nanotubes (CNTs) or an organically modified montmorillonite (Cloisite 15A), both previously modified by plasma treatment to introduce polar moieties. The nanofillers were fully characterized by Raman spectroscopy, XPS, FT-IR and XRD, demonstrating their effective modification with oxygenated groups. The nanocomposites were prepared by melt processing in order to obtain films and fibres. The mechanical tests carried out on the nanoc…

Facile and novel synthesis of Graphene oxide/Silica nanohybrids with tunable properties

Integrated ternary bionanocomposites with superior mechanical performance via the synergistic role of graphene and plasma treated carbon nanotubes

Abstract Herein, we prepared an integrated ternary bionanocomposite based on polylactic acid (PLA) as a host polymer and two different forms of carbon fillers, i.e. graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs), used simultaneously at extremely low concentrations, relying on the synergistic effect of CNT and graphene nanoreinforcement and a novel, multi-step procedure to achieve a high level dispersion. The results indicated that this multi-step approach allows stiffness increments up to +66%, with simultaneous enhancement of tensile strength (up to +44%), and elongation at break (up to +36%) with respect to neat PLA, by adding an extremely low content (0.5 wt%) of a hybrid comb…

An innovative route to prepare in situ graded crosslinked PVA graphene electrospun mats for drug release

We present a fast, one step method to obtain PVA/graphene/chlorhexidine nanofibrous membranes, with a crosslinking gradient along their cross-section. Briefly, polymeric solutions were electrospun onto a heated plate, enabling the in situ crosslinking of PVA macromolecules. Of course, the crosslinking degree of such structures was found to decrease upon the distance from the plate during deposition. The outcomes reveal the crucial role of graphene, capable of promoting heat transfer throughout the entire structure, thus leading to 70-80% crosslinking degrees and preventing delamination issues. Such membranes were compared to untreated and oven thermally treated ones, and a robust relationsh…

Effect of alkyl derivatization of gellan gum during the fabrication of electrospun membranes

Electrospun nanofibers based on polysaccharides represent a consolidated approach in Tissue Engineering and Regenerative Medicine (TERM) and nanomedicine as a drug delivery system (DDS). In this work, two chemical derivatives of a low molecular weight gellan gum (96.7 kDa) with aliphatic pendant tails were processed by electrospinning technique into non-woven nanofibrous mats. In order to generate spinnable blends, it was necessary to associate poly vinyl alcohol (PVA). The relationships between the physicochemical properties and the processability via electrospinning technique of gellan gum alkyl derivatives (GG-C8 and GG-C12 having a degree of alkyl chain derivatization of 17 mol % and 1…

Plasma Functionalization of Multiwalled Carbon Nanotubes and Their Use in the Preparation of Nylon 6-Based Nanohybrids

The possibility to obtain carbon nanotubes (CNT)/polyamide 6 composites with excellent mechanical properties in a simple, industrially scalable way is investigated. Commercial CNTs are treated by plasma while changing some key parameters (exposure time, plasma power, type of gas) in order to optimize the process and to achieve a sufficient degree of functionalization. The treated samples are characterized by Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The most interesting samples are selected to be used as reinforcing fillers, in different concentrations, in a polyamide 6 matrix. The mechanical tests show a dramatic increase of both tens…

PREPARAZIONE DI MATERIALI POLIMERICI MULTIFUNZIONALI A BASE DI NANOTUBI DI CARBONIO

Structure-property relationship of PLA-Opuntia Ficus Indica biocomposites

Abstract In this work, a lignocellulosic flour was achieved by grinding the cladodes of Opuntia Ficus Indica and then added to a poly-lactic acid (PLA) in order to prepare biocomposites by melt processing. The influence of filler content and size on the morphological, rheological, and mechanical properties of the green composites was assessed. Moreover, solvent-aided filler extraction enabled to evaluate the homogeneity of filler dispersion, as well as the effect of processing on the geometrical features of the fillers. The experimental data obtained by tensile tests proved to be remarkably higher than those predicted by Halpin–Tsai model, presumably due to the capability of the polymer to …

A Novel Graphene Oxide-Silica Nanohybrid, Highly Functionalized by Organic Fluorotails

GO-based composites have attracted increasing attention due to their improved properties: in this context Silica-GO nanohybrids are currently used in many fields, ranging from biomedicine to optoelectronics. In recent years growing interest of the materials community has been posed on the functionalization of graphene materials with fluorine: Fluorinated graphene oxide has been proven to be the first carbon material for Magnetic Resonance Imaging without the addition of magnetic nanoparticles,1 moreover, has proven to absorb NIR-laser energy and efficiently transform it into heat, so that fluorinated graphene oxide has been suggested as a contrast agent for MRI, ultrasound and photoacoustic…

GREEN COMPOSITES BASED ON BIODEGRADABLE POLYMERS AND WOOD FLOUR

Effect of graphene and fabrication technique on the release kinetics of carvacrol from polylactic acid

Abstract Porous membranes and thin films containing poly-lactic acid (PLA), carvacrol (CRV) and graphene nanoplatelets (GNP) were fabricated by electrospinning and solvent casting at different formulations. The systems were characterized from a mechanical, morphological, calorimetric and spectroscopic point of view. CRV release as a function of time was studied and a mathematical model was used to fit and interpret the data in order to investigate the release mechanism. The results indicate that the incorporation of GNP generally determined a simultaneous strengthening, stiffening and toughening effect, while preserving a good ductility. Furthermore, integrating GNP allowed tuning the amoun…

Graphene oxide-silica nanohybrids as fillers for PA6 based nanocomposites

Graphene oxide (GO) was prepared by oxidation of graphite flakes by a mixture of H2SO4/H3PO4 and KMnO4 based on Marcano's method. Two different masterbatches containing GO (33.3%) and polyamide-6 (PA6) (66.7%) were prepared both via solvent casting in formic acid and by melt mixing in a mini-extruder (Haake). The two masterbatches were then used to prepare PA6-based nanocomposites with a content of 2% in GO. For comparison, a nanocomposite by direct mixing of PA6 and GO (2%) and PA6/graphite nanocomposites were prepared, too. The oxidation of graphite into GO was assessed by X-ray diffraction (XRD), Micro-Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectrosco…

A rapid and eco-friendly route to synthesize graphene-doped silica nanohybrids

International audience; In the present study, the possibility to synthesize graphene oxide (GO)-based nanohybrids with pure and O2-doped silica nanoparticles by a rapid and easy hydrothermal process has been explored. The nanohybrids were prepared by varying the type of silica nanoparticles (average diameter 7 nm or 40 nm) and the silica/GO weight ratio. All the materials were fully characterized by spectroscopic and morphological techniques.The experimental results revealed that it is possible to tune the characteristics of the obtained nanohybrids, such as morphology and amount of ester/ether linkages upon varying the preparation parameters, together with the nanosilica's typology and the…

A novel approach to prevent graphene oxide re-aggregation during the melt compounding with polymers

Abstract The technology for the preparation of polymer-GO nanocomposites was investigated by studying the structure-properties relationships of two different systems, based on PA6 and EVA, fabricated by using different preparation methods, i.e. melt mixing, wet phase inversion, and the combination of the two. The morphology of nanocomposites resulted dramatically influenced by the technique adopted and showed to be the critical variable affecting the physical properties of the materials. Finally, the mechanical and dynamic-mechanical of the nanocomposites were improved by using the hybrid technique combining the two procedures.

Tunable release of Chlorhexidine from Polycaprolactone-based filaments containing graphene nanoplatelets

Abstract Graphene nanoplatelets (GNP) as fillers and Chlorhexidine (CHX), as an antibacterial agent, were incorporated in a polycaprolactone (PCL) matrix and processed into filaments by melt spinning. The influence of both drawing and formulation on the processability, spinnability, mechanical properties and release behaviour of these materials were deeply investigated by performing rheological, morphological analysis, tensile tests, and by measuring the cumulative release of CHX in PBS at 37 °C. Furthermore, Korsmeyer–Peppas model was adopted to study the kinetics release mechanism. The results showed that adding GNP did not alter the processability and spinnability of the systems. Further…

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 an…

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&reg

PLA graphene nanoplatelets nanocomposites: Physical properties and release kinetics of an antimicrobial agent

Abstract Graphene nanoplatelets (GnP) as filler and ciprofloxacin (CFX) as biocide were incorporated via melt-compounding into poly(lactic acid) (PLA) to obtain biopolymer-based nanocomposites with antimicrobial properties. GnP were added with the aim of improving the mechanical properties of the antimicrobial system and tuning the drug release. The obtained systems were mechanically characterized in tensile mode by quasi-static and dynamic mechanical tests. Furthermore, rheological measurements were performed. The morphology of the samples was analyzed through scanning electron microscopy (SEM). Moreover, a mathematical model, i.e. power law model, was used to fit the release data in order…

Polyamide 6/Graphene Oxide Nanohybrids

IMPROVED STABILITY OF GRAPHENE OXIDE-SILICA NANOHYBRIDS AND RELATED POLYMER-BASED NANOCOMPOSITES

Although its promising properties make the graphene oxide (GO) very interesting as filler for polymer matrices, some problems related to its thermal stability in the region which ranges from 80 to 200 °C, are crucial for the possibility to melt process GO together with practically all the polymers [1,2]. Moreover, above 100 °C GO lamellae were found to become stacked. In this work, two different ways to preserve the GO structure and ensure its dispersion within different polymer matrices have been investigated and schematized in Fig. 1. Exfoliation plays a key-role in the achievement of good mechanical properties since it preserves the GO from both stacking phenomena. The capability of sili…

Plasma Modification of CNTs and Their Use in the Preparation of PA6/CNT Nanocomposites

Structural and thermal stability of graphene oxide-silica nanoparticles nanocomposites

Abstract The investigation of the thermal stability up to 400 °C of Graphene Oxide (GO) and GO-silica nanoparticles (n-SiO2) composites prepared by direct mixture of GO and n-SiO2 is reported. Using Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, Energy Dispersive X-ray analysis, Atomic Force Microscopy, Raman and Infrared absorption measurements a thorough characterization of the prepared materials is carried out. By deepening the changes induced in the 2D Raman spectral region of GO at about 2900 cm−1 the comprehension of an interplay, driven by the thermally induced changes of the material, between inter-valley and intra-valley vibrational transitions is elucidated. This …

Polysaccharide nanocrystals as fillers for PLA based nanocomposites

The development of green nanocomposites based on biopolymers and bio-based nanofillers has attracted over the recent years the attention of academic and industrial research. Indeed, these nanocomposites could replace some oil-derived polymers and thus helping to overcome environmental problems. In this regard, PLA as matrix and polysaccharide nanocrystals as fillers are the most promising components to obtain high-performance green bio-nanocomposites suitable for different applications, particularly for packaging and biomedical applications. Indeed, at present, due to its processability, mechanical and biological properties, as well as its commercial availability, poly(lactic acid) (PLA) po…

Hybrid biocomposites based on polylactic acid and natural fillers from Chamaerops humilis dwarf palm and Posidonia oceanica leaves

AbstractPlatelet-like and fibrous lignocellulosic fillers were achieved from the leaves of Chamaerops humilis (CHL) and Posidonia oceanica (POL) and used as a hybrid reinforcement for a polylactic acid (PLA) matrix at three different loading levels (from 5 to 20%). The materials were fully characterized from a morphological, physicochemical, mechanical, and dynamic-thermomechanical point of view. When compared to their counterpart containing either CHL or POL only, the resulting hybrid biocomposites showed the highest mechanical properties, with strengthening and stiffening effects respectively up to 120% and 50% higher than those expected from the linear combination of the two, and higher …

Scaffold con gradiente della dimensione dei pori per la migrazione selettiva di cellule eterotipiche

Polymer-based 'green' composites

Effetto della preparativa sulle proprietà di nanocompositi a base di ossido di grafene

Carbon nanotubes modification by plasma treatment

Advanced piezoresistive sensor achieved by amphiphilic nanointerfaces of graphene oxide and biodegradable polymer blends

This work focuses on the preparation of a piezoresistive sensor device, by exploiting an amphiphilic sample of graphene oxide (GO) as a compatibilizer for poly (lactic acid) (PLA)-Poly (ethylene-glycol) (PEG) blends. The presence of GO determined a high stiffening and strengthening effect, without affecting toughness, and allowed a good stability of mechanical properties up to 40 days. Moreover, GO endowed the materials with electrical properties highly sensitive to pressure and strain variations: the biodegradable pressure sensor showed a responsivity of 35 μA/MPa from 0.6 to 8.5 MPa, a responsivity around 19 μA/MPa from 8.5 to 25 MPa. For lower pressure values (around 0.16–0.45 MPa), inst…

EFFETTO DI TIPOLOGIA E FUNZIONALIZZAZIONE DI NANOTUBI DI CARBONIO SULLE PROPRIETA’ DI FIBRE A MATRICE POLIAMMIDICA

Si riportano i risultati relativi all'utilizzo di due campioni di CNT: uno commerciale (purezza 90%, L/D ≈ 50) ed uno sintetizzato e purificato ad hoc (purezza 99%, L/D ≈ 500) come filler per la realizzazione di fibre a matrice poliammidica. In particolare, si è investigato l’effetto della funzionalizzazione mediante plasma sulle proprietà reologiche, meccaniche ed elettriche delle fibre ottenute. La quantità di carica (2%) e le condizioni operative di trattamento al plasma sono state ricavate da studi precedenti. Le misure di viscosità elongazionale condotte sui campioni a base di CNT tal quali e funzionalizzati hanno messo in luce come l’introduzione della carica comporti un netto increme…

Mechanical behavior of polylactic acid/polycaprolactone porous layered functional composites

Abstract Biopolymeric porous devices exhibiting graded properties can play a crucial role in several fields, such as tissue engineering or controlled drugs release. In this context, the gradient of a specific property can be achieved by developing porous laminates composed by different types of materials. This work presents for the first time a multi-phasic porous laminate based on polycaprolactone (PCL) and polylactic acid (PLA) prepared by combining melt mixing, compression molding and particle leaching. All the materials were characterized from a morphological and a mechanical point of view. The results put into evidence the possibility to tune and to predict the mechanical properties by…

Statistical analysis of mechanical and dynamic-mechanical properties of PC/CNTs nanocomposites.

Rapid and eco-friendly synthesis of graphene oxide-silica nanohybrids

Modelling the structure-property relationships of high performance PBAT-based biocomposites with natural fibers obtained from Chamaerops humilis dwarf palm

Two fibrous fillers were achieved from stalks and leaves of Chamaerops humilis dwarf palm and tested as reinforcing agents for poly(butylene adipate co-terephthalate) (PBAT)-based composites. The influence of filler type and content on the morphomechanical properties of the green composites was assessed. The outcomes of tensile tests pointed out that both fillers are strong candidates to overcome the two main limiting aspects of PBAT, that is, the lack of both stiffness and cost-effectiveness, while preserving its stretchability and environmental sustainability. The remarkable stiffness increments (up to 300%), combined with fair retention of stretchability (33%) and doubled resistance, led…

Physical properties of green composites based on poly-lactic acid or Mater-Bi® filled with Posidonia Oceanica leaves

Abstract This work focuses on the evaluation of Posidonia Oceanica leaves as effective reinforcing agent for ecofriendly, fully biodegradable polymer composites. Posidonia leaves were washed, ground and sieved in order to achieve two different size distributions and aspect ratios. They were then added to either a stiff or a ductile biodegradable polymer matrix, respectively poly-lactic acid (PLA) and MaterBi® (MB), at two different filler contents (10 wt% and 20 wt%). The materials were fully characterized from a spectroscopic, morphological, rheological, and mechanical point of view. In particular, the outcomes of tensile tests were statistically analyzed by using a Full Factorial Design i…

High performance PA6/CNTs nanohybrid fibers prepared in the melt

Commercial and home-made carbon nanotubes (CNTs) were plasma treated under oxygen atmosphere and then added to polyamide 6 (PA6) in order to prepare fibres by melt spinning. For comparison, pristine nanofillers were used too. The effect of functionalization and of filler characteristics on the morphological, rheological, mechanical and electrical properties of the fibres was studied by TEM and SEM, rheological measurements, tensile and electrical conductivity tests. The results demonstrated that the functionalization led to a better mechanical performance and the morphological analysis confirmed that the adhesion, the dispersion and the alignment of the nanotubes within the polymer matrix w…

Processing-structure-property relationships of electrospun PLA-PEO membranes reinforced with enzymatic cellulose nanofibers

Abstract Three different solvent mixtures were used to prepare electrospun membranes based on polylactic acid (PLA), polyethylene oxide (PEO) and enzymatic cellulose nanofibers (CNF). The materials were characterized from a morphological, spectroscopic, mechanical and rheological point of view. Furthermore, swelling test were performed in order to assess the water uptake of each sample. The results put into evidence that the choice of the solvents affects the structure and the properties of the membranes. Among the protocols tested, using chloroform/acetone/ethanol mixture was found to allow a high degree of CNF dispersion and a good electrospinnability of polymer solutions. These features …

Preparation and mechanical characterization of polycaprolactone/graphene oxide biocomposite nanofibers

Biocomposite nanofiber scaffolds of polycaprolactone (PCL) filled with graphene oxide (GO) were prepared using electrospinning technology. Morphological and mechanical properties of the scaffolds were characterized in dry and wet environment. The results showed that the successful incorporation of GO nanosheets into PCL polymer nanofibers improved their mechanical properties. Furthermore it was demonstrated the higher performance achieved when GO is filled at low concentration in the nanofibers.

Optimization of two-step techniques engineered for the preparation of polyamide 6 graphene oxide nanocomposites

Abstract Different processing conditions to achieve polyamide 6 (PA6)-graphene oxide (GO) nanocomposites were investigated. GO was pre-dispersed in PA6 by three different solvent-based methods and, further, melt processed to prepare nanocomposites at two different loading levels, namely 2 and 5 wt.%. The evolution of rheological and mechanical properties was analyzed by investigating eventual changes in the microstructure and polymer crystallinity, aiming at providing a detailed processing-structure-properties relationship for these systems.

MULTIFUNCTIONAL FIBERS BASED ON POLYAMIDE 6 AND PLASMA FUNCTIONALIZED CARBON NANOTUBES MoDeSt 2012 Conference, Praga, 2-6 Settembre 2012.

Commercial (CNT 1) and ad hoc synthesized carbon nanotubes (CNT 2) were plasma treated under oxygen atmosphere and then added to polyamide 6 (PA 6) in order to prepare multifunctional fibres by melt spinning. For comparison, pristine nanofillers were used too. The effect of functionalization and of filler characteristics on the morphological, rheological, mechanical and electrical properties of the fibers was studied by TEM and SEM, rheological measurements, tensile tests and electrical conductivity tests. The amalysis of Raman spectra put into evidence that the intensity of D-band (correlated with the degree of functionalization by the different vibration mode of carbon atoms in the presen…

PLA-based functionally graded laminates for tunable controlled release of carvacrol obtained by combining electrospinning with solvent casting

Abstract A novel approach was designed to fabricate high-added value manufacts, starting from cost-effective materials and combining well-known processing techniques. Bi- and three-layered, functionally graded laminates were achieved by direct electrospinning onto dense substrates. The architecture of each multilayer comprises a dense layer formed by solvent casting, which is constituted by polylactic acid (PLA) and carvacrol, and one or two electrospun fibrous skin layers, consisting of PLA only. Processing-structure-properties relationships of such materials were investigated. As regards mechanical behavior, the amount of fibrous PLA layers determined an increase of stiffness from 20 to 3…

Statistical analysis of the performances of PC/CNTs nanocomposites

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 t…

Electrospun PCL/GO-g-PEG structures: Processing-morphology-properties relationships

Abstract Polycaprolactone (PCL) biocomposite nanofiber scaffolds with different concentrations of graphene oxide (GO) and GO surface grafted with poly(ethylene glycol) (GO-g-PEG) were prepared by electrospinning. Morphological, mechanical as well as wettability characterizations of electrospun nanofibers were carried out. Results showed that the average diameter of PLA/GO electrospun nanofibers decreased upon increasing the filler content. Differently, the diameter increased while using GO-g-PEG. Both nanofillers enhanced the electrospun PCL hydrophilicity even if PCL/GO-g-PEG samples exhibited improved wettability. The Young moduli of the composite nanofiber mats were improved by adding GO…

PEGylated graphene oxide (GO-PEG) as new carrier for chemotherapeutic agent delivery

Graphene, a single layer of sp2 -hybridized carbon atoms arranged in a honeycomb two-dimensional (2-D) crystal lattice, has evoked enormous interest throughout the scientific community since its first appearance in 2004. Due to its unique structure and geometry, graphene possesses remarkable physical–chemical properties (including large specific surface area and biocompatibility) that enable it to be an ideal material for several of applications, ranging from quantum physics, nanoelectronics, energy research, catalysis and engineering of nanocomposites and biomaterials. In the area of nanomedicine, graphene and its derivatives can be exploited for a broad range of applications, including a …

Mechanical behaviour of Mater-Bi/wood flour composites: a statistical approach

Interest in biocomposites (lignocellulosic filled biopolymers) started in the 90s, due to environmental advantages, related to the full biodegradability of both matrix and filler, economical issues (organic fillers usually come from sawmill or agriculture wastes) and aesthetical issues (wood filled biopolymers could be particularly pleasant if used for indoor furnishing and automotive interior). In this work, a method for a systematic study of the properties of Mater-Bi®/wood flour composites is presented. A two-level full factorial model was built. It allows investigating the effects of multiple operative variables on the observed properties, their contributions, their optimal combinations…

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 c…

Multifunctional fibers based on polyamide 6 and plasma functionalized carbon nanotubes.

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…

Synthesis and self-assembly of a PEGylated-graphene aerogel

Abstract In the frame of this work, we present, for the first time, the synthesis and self-assembly of an aerogel built by graphene oxide-polyethylene glycol. The synthetic route involves at first the coupling of GO with an amino-terminated polyethylene glycol sample by carbodiimide in aqueous environment, and the subsequent conversion of the hydrogel achieved into an aerogel via freeze-drying. The 3D PEGylated graphene-based aerogel, characterized by spectroscopic, morphological, structural and mechanical analyses, displays an ultralight and highly porous (99.7%) network and possesses high mechanical properties together with a good biocompatibility.

Nanopiattaforme di Ossido di Grafene perfluorurate: materiali biocompatibili con affinità per l'ossigeno

L’attacco covalente di molecule perfluorurate su ossido di graphene (GO) via sostituzione nucleofila aromatica ha consentito una facile funzionalizzazione delle lamelle di GO.1,2 La performance delle nanopiattaforme perluorurate (GOF) nell’uptake e rilascio di ossigeno è stata valutata in condizioni di pH fisiologico a differenti concentrazioni e temperature, dimostrando una maggiore affinità del materiale perfluorurato GOF rispetto al GO pristino. Anche a basse concentrazioni GOF ha mostrato valori di uptake di ossigeno a saturazione e velocità di diffusione superiori ad altri materiali proposti in letteratura per ingegneria tissutale, per l’ossigenazione cellulare durante la rigenerazione…

A green method to prepare nanosilica modified graphene oxide to inhibit nanoparticles re-aggregation during melt processing

Abstract A graphene oxide-silica nanohybrid (GOS), self-assembled into a lasagna -like structure, was prepared in water and used as a filler for the melt preparation of polyamide 6 (PA6)-based nanocomposites. For sake of comparison, PA6-based materials were prepared under the same processing conditions by adding GO only or a physical mixture of GO and silica (GO+S). All the materials were characterized from a morphological, spectroscopic, thermal, dynamic-mechanical (DMA) and mechanical point of view. For all the nanocomposites, the interphase was studied either by analyzing loss factor plots coming from DMA measurements and by implementing a novel approach, i.e. combining solvent extractio…

Green Nanocomposites-Based on PLA and Natural Organic Fillers

Over the past decades, many efforts have been carried out for the development of novel green nanocomposites based on biopolymers and natural organic nanofillers. Indeed, these nanocomposites could replace some oil-derived polymers and thus helping to overcome environmental problems. In this regard, poly (lactic acid) (PLA) as matrix and polysaccharide nanocrystals (cellulose, chitin, and starch) as bio-based nanoreinforcements are the most promising components to obtain high-performance green nanocomposites. This chapter covers the basic features of PLA and polysaccharide nanocrystals derived from biomass-based raw materials such as cellulose, chitin, and starch. In particular, this chapter…

Perfluorocarbons–graphene oxide nanoplatforms as biocompatible oxygen reservoirs

Abstract 3-Pentadecafluoroheptyl,5-perfluorophenyl-1,2,4-oxadiazole (FOX) molecules were attached onto a graphene oxide (GO) via a facile aromatic substitution in alkaline environment. This approach allows achieving high degree of functionalization under mild conditions. The covalent attachment of perfluoromoieties onto GO lamellae was confirmed by spectroscopic analyses. The performance of these nanoplatforms (GOF) as oxygen reservoirs was assessed at different concentrations and temperature. The results revealed that under physiologic conditions GO and FOX synergistically operate for increasing oxygen uptake and release, either from a thermodynamic and a kinetic point of view. Even at low…

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…

CORRELATION BETWEEN THE CHEMICAL-PHYSICAL PROPERTIES OF CNT AND MACROSCOPIC PROPERTIES OF RELATED NANOCOMPOSITES: A STATISTICAL APPROACH

In the frame of this work, two different samples of CNTs, namely CNT 1 and CNT 2, were synthesized [1] with different degree of purity and aspect ratio and used as fillers either without any treatment or after a plasma-oxidation, to prepare polycarbonate (PC)-based nanocomposites by melt mixing. The influence of plasma treatment, filler content and type of CNTs on the mechanical, dynamic-mechanical, and electrical properties of the materials was assessed by a two level full factorial design. The morphological analysis carried out by SEM and TEM evidenced the formation of a nanohybrid structure when oxidized CNTs were used as filler. Generally speaking, CNT 2 showed the best dispersion and t…

Realizzazione di nanocompositi a base di PA6 e CNT funzionalizzato al plasma

Ecocompositi MaterBi (R)/Farina di legno: ottimizzazione delle proprietà attraverso analisi statistica

Ionic tactile sensors as promising biomaterials for artificial skin: Review of latest advances and future perspectives

Abstract Ionic tactile sensors (ITS) are an emerging subfield of wearable electronics, capable of mimicking the human skin, including not only the typical anisotropic structure, mechanical behaviour, and tactile functions but even the mechanosensitive ionic channels that are crucial for the human sense of touch. With the rapid development of intelligent technology, such bioinspired materials constitute the core foundation of intelligent systems and are a candidate to be the next generation e-skins, offering a more accurate and evolved biointerface. In the latest years, a wealth of novel ultra-stretchable ITS was proposed, progressively refining the choice of soft materials, including ion ge…

Synthesis of a fluorinated graphene oxide-silica nanohybrid: Improving oxygen affinity

An easy method to achieve a fluorinated graphene oxide–silica nanohybrid (GOSF) is presented. Graphene oxide (GO) was synthesized by Hummer's modified method, the GO–silica nanohybrid (GOS) was obtained via Fischer esterification, the fluorinated moiety (3-pentadecafluoroheptyl-5-perfluorophenyl-1,2,4-oxadiazole) was introduced by nucleophilic substitution operated by the hydroxyl functionalities onto the GOS surface. Full characterization of the new materials confirmed the formation of covalent bonds between the graphene oxide/silica hybrid matrix and the fluorinated moieties. The proposed methodology offers an easy way to get fluorinated carbon/silica hybrid nanomaterials avoiding the har…

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 distr…

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…

Bilayer biodegradable films prepared by co-extrusion film blowing: Mechanical performance, release kinetics of an antimicrobial agent and hydrolytic degradation

Abstract Bilayer biodegradable, eco-friendly films were prepared by co-extrusion film blowing, coupling polylactic acid (PLA) and Bio-flex ® (BIO). Furthermore, in the PLA layer, carvacrol (CRV) was added as a natural antimicrobial additive, whereas a nanoclay (D72T) was integrated to protect CRV from volatilization and to modulate release. The materials were analyzed by morphological, chemical-physical, mechanical testing. Furthermore, CRV release and degradation tests were performed. The results pointed out that coupling the two matrices allows gathering the stiffness of PLA with the ductility of BIO. Furthermore, the interlayer adhesion is promoted by CRV. D72T exerts a key-role in avoid…

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 …

PHOTO-OXIDATION OF PA6/GRAPHENE OXIDE FILMS

Graphene oxide (GrO) was synthesized with Marcano’s method [1] and added at 0.5 and 1 wt% loading content to a polyamide 6 (PA6). In particular, three different techniques have been used for the preparation of the nanocomposites: (i) melt blending in a batch mixer, (ii) solvent casting in formic acid, (iii) preparation of a masterbatch by solvent casting and further melt processing. The films (80 m) were photo-oxidized in a QU-V chamber up to about 100 hours. The effect of filler content and preparation technique on the photo-stability of the nanocomposites has been followed by monitoring the change of the mechanical and spectroscopic properties undergone upon artificial exposure to UV-B l…

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…

Orientation and exfoliation of clay nanoparticles in the spinning of a nanobiocomposite sample

Polymer nanobiocomposites represent a new group of materials filled with inert nanosized particles that show very interesting properties with respect to the matrix and the same biodegradability of the matrix. In this work we have studied the effect of the elongational flow on the morphology and dynamic-mechanical properties of a new nanobiocomposite made by a matrix of biodegradable PLA and a filler of organomodified montmorillonite.

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…

Melt-spun conductive fibers containing functionalized CNTs

Plasma Modification of MWCNTs and Their Use in the Preparation of PA6/MWCNT Nanocomposites

Synthesis and characterization of PEGylated graphene oxide for sorafenib modified release

Concept Graphene, a single layer of sp2-hybridized carbon atoms arranged in a honeycomb two-dimensional (2-D) crystal lattice, has evoked enormous interest throughout the scientific community since its first appearance in 2004. Due to its unique structure and geometry, graphene possesses remarkable physical-chemical properties (including large specific surface area and biocompatibility) that enable it to be an ideal material for several applications, ranging from quantum physics, nanoelectronics, energy research, catalysis and engineering of nanocomposites and biomaterials. In the area of nanomedicine, graphene and its derivatives can be exploited for a broad range of applications, includin…

Pore size graded scaffold for selective cellular permeation

Hydrolytic degradation of PLA/Posidonia Oceanica green composites: A simple model based on starting morpho-chemical properties

Abstract In this work, we studied the degradability of PLA-based biocomposites containing Posidonia Oceanica flour at different loading levels and aspect ratios. Hydrolytic tests were carried out in neutral (pH = 7.4) and alkaline (pH = 10) environment. Time-dependent evolution of some key features, including residual mass and solution uptake, was monitored, and correlated with the changes observed in both morphology and chemical structure of the matrix. The results pointed out that biocomposites degraded much faster than neat PLA in both conditions, up to lose 70% of their initial weight after 1000 h immersion. A complex mechanism was unveiled, evidencing the crucial role of the fillers, c…

Lignocellulosic fillers and graphene nanoplatelets as hybrid reinforcement for polylactic acid: Effect on mechanical properties and degradability

Abstract This work investigates the effect of adding relatively low amounts of graphene nanoplatelets (GNP) to a biocomposite based on polylactic acid (PLA) and a lignocellulosic filler achieved by grinding Posidonia Oceanica leaves (Posidonia flour, PF). The ternary composites were prepared by melt extrusion and characterized from a morphological and mechanical point of view. Furthermore, hydrolytic degradation tests were performed under acidic, neutral and alkaline environment up to 900 h. Density measurements enabled to assess the degree of intraphase, i.e. the capability of polymer macromolecules to enter the voids of PF and a modified Halpin-Tsai model was presented and used to fit exp…

Effect of adding wood flour to the physical properties of a biodegradable polymer

Wood flour/polymer composites (WPC) gained a significant interest during the last decades, due to several advantages related to the use of a natural-organic filler rather than an inorganic-mineral one. However, most of the studies have been performed on composites based on polyolefin matrices. A further step is the use of biodegradable polymers instead of traditional ones. In this work, wood flour (WF), under the form of short fibers, with two different sizes (coarse and fine) was added to a corn starch based biodegradable polymer of the Mater-Bi family. The effect of WF size, WF content, thermal treatment on the mechanical properties was investigated. The tensile mechanical tests showed an…

Use of carbon nanotubes functionalized via plasma for the preparation of PA6-based nanohybrids

Effect of an organoclay on the photochemical transformations of a PBAT/PLA blend and morpho-chemical features of crosslinked networks

Abstract In this work, we report the effect of an organoclay on the photochemical weathering of nanocomposites based on a poly(butylene adipate-co-terephthalate) (PBAT)/poly(lactic acid) (PLA) blend. The evolution of physicochemical properties was monitored by integrating spectroscopic, mechanical, and morphological analyses. A robust relationship was found between the molecular transformations of the polymer macromolecules and the morpho-mechanical properties of irradiated films. Moreover, the analysis of insoluble fractions extracted from nanocomposites pointed out that free-standing, porous structures, displaying an unprecedented thickness as great as 100 µm, were formed, thus unambiguou…

Comportamento di nanocompositi PA6/CNT in flusso elongazionale non isotermo

Si sono preparate fibre a matrice poliammidica caricate con CNT. Sono state utilizzate due diverse tipologie di CNT a differente fattore di forma e grado di purezza, ossidate mediante plasma di ossigeno. Le misure di viscosità elongazionale hanno evidenziato che l’introduzione della carica comporta un incremento della MS a fronte di una diminuzione della BSR per tutti i materiali caricati. La tipologia e la funzionalizzazione dei CNT hanno delle notevoli ricadute sul diverso comportamento reologico. Studi morfologici hanno evidenziato che dopo la funzionalizzazione si registrano livelli di dispersione, allineamento e adesione interfacciale più alti. La natura delle interazioni matrice-caric…

Synthesis of a biocompatible aerogel based on graphene oxide and a modified polyethylene glycol

The synthesis and self-assembly of a 3D aerogel built by graphene oxide (GO) and a modified polyethylene glycol (PEG) was achieved by a multi-step synthetic procedure, involving the preparation of an amino-terminated PEG (PEG-NH2) and the subsequent coupling with GO by carbodiimide in water, exploiting the carboxyl and epoxy moieties of GO and –NH2 terminations of the biopolymer. The resulting nanohybrid hydrogel was successively converted into an aerogel via dialysis plus freeze-drying [1] and fully characterized. FTIR, Raman, XPS, XRD and BET measurements were performed to confirm the successful modification for each reaction step, while morphological, mechanical and hemolytic tests were …