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…

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…

Green composites for fertilizer controlled release produced by compression molding and FDM

Excessive fertilization causes ecological problems due to leaching issues. To solve this problem and promote agriculture sustainability an innovative green composite for controlled release fertilizers was produced by adding NPK fertilizer flour to a biodegradable polymer with or without Opuntia Ficus Indica (OFI) particles. Six formulations were produced and employed for the fabrication of devices both for compression molding (CM) and fused deposition modeling (FDM). Both fillers displayed a good dispersion in the composites, excellent adhesion with the polymeric matrix and effectively acted as reinforcement. The decrease of NPK release rate (up to 30 days) was achieved using whole composit…

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 …

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…

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

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 …

Hedysarum coronarium-Based Green Composites Prepared by Compression Molding and Fused Deposition Modeling

In this work, an innovative green composite was produced by adding Hedysarum coronarium (HC) flour to a starch-based biodegradable polymer (Mater-Bi®, MB). The flour was obtained by grinding together stems, leaves and flowers and subsequently sieving it, selecting a fraction from 75 μm to 300 μm. Four formulations have been produced by compression molding (CM) and fused deposition modeling (FDM) by adding 5%, 10%, 15% and 20% of HC to MB. The influence of filler content on the processability was tested, and rheological, morphological and mechanical properties of composites were also assessed. Through CM, it was possible to obtain easily homogeneous samples with all filler amounts.…

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…

OPUNTIA FICUS INDICA/MATER-BI® BASED GREEN COMPOSITES FOR FERTILIZER CONTROLLED RELEASE DEVICES PRODUCTION

3D PRINTED GREEN COMPOSITES BASED ON POLYMERIC MATRICES AND ANCHOVY FISHBONE WASTES

Structure–property relationship and controlled drug release from multiphasic electrospun carvacrol-embedded polylactic acid/polyethylene glycol and polylactic acid/polyethylene oxide nanofiber mats

Electrospinning technologies gained considerable interest over the last decade. In this study, it is proposed a systematic study of polylactic acid/polyethylene glycol (PLA/PEG) and polylactic acid/polyethylene oxide (PLA/PEO) electrospun blends at different concentrations. The effect of blend composition and PEG molecular weight on the morphological and mechanical properties of the mats was evaluated. Furthermore, the kinetic release of carvacrol as model drug in phosphate buffer saline at 37℃ was studied and the data were then fitted using an exponential model. The scanning electron microscopy revealed that the morphology of the mats was strongly dependent on the relative ratio PLA:PEG, …

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…

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 …

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…

A New Methodological Approach to Correlate Protective and Microscopic Properties by Soft X-ray Microscopy and Solid State NMR Spectroscopy: The Case of Cusa’s Stone

Hydrophobic treatment is one of the most important interventions usually carried out for the conservation of stone artefacts and monuments. The study here reported aims to answer a general question about how two polymers confer different protective performance. Two fluorinated-based polymer formulates applied on samples of Cusa’s stone confer a different level of water repellence and water vapour permeability. The observed protection action is here explained on the basis of chemico-physical interactions. The distribution of the polymer in the pore network was investigated using scanning electron microscopy and X-ray microscopy. The interactions between the stone substrate and the protective…

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…

SVILUPPO DI SISTEMI CON STRUTTURE COMPLESSE A BASE BIOPOLIMERICA REALIZZATI ATTRAVERSO PROCESSI COMBINATI IN MULTI- O IN ONE-STEP

L'analisi dello stato dell'arte suggerisce che la combinazione di processi di produzione, solitamente impiegati per l’elaborazione di strutture differenti, comporta la produzione di dispositivi a base biopolimerica con strutture complesse e proprietà rilevanti. L'obiettivo di questo lavoro di ricerca è stato quello di esplorare i diversi vantaggi dei metodi di elaborazione combinati sia in one-step che in two-steps. In particolare, sono state testate diverse combinazioni di processing al fine di ottenere dispositivi a base biopolimerica con strutture e proprietà non ottenibili da singoli processi, trattamenti o materiali. Ogni dispositivo è stato caratterizzato al fine di comprendere le rel…

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…

Biodegradable Membrane with High Porosity and Hollow Structure Obtained via Electrospinning for Oil Spill Clean-up Application

The use of biodegradable polymers for the production of membranes to be used in wastewater treatment has attracted increasing interest considering the possibility of reducing the risk of second pollution. In this work, porous fibrous membranes based on polylactic acid and polyethylene oxide (PEO) blends were prepared. The solutions were electrospun using two approaches: (i) conventional coaxial electrospinning followed by leaching treatment (double-step, DS); (ii) coaxial wet electrospinning with in situ leaching (single-step, SS). By varying PEO type and processing method it was possible to control membranes structure and porosity. DS leaching treatment lead to surface porosity (i.e. shell…

Opuntia Ficus Indica based green composites for NPK fertilizer controlled release produced by compression molding and fused deposition modeling

Excessive fertilization causes ecological problems due to leaching issues. To solve this problem and promote agriculture sustainability an innovative green composite for controlled release fertilizers was produced by adding NPK fertilizer flour to a biodegradable polymer with or without Opuntia Ficus Indica (OFI) particles. Six for- mulations were produced and employed for the fabrication of devices both for compression molding and fused deposition modeling (FDM). Both fillers displayed a good dispersion in the composites, excellent adhesion with the polymeric matrix and effectively acted as reinforcement. The decrease of NPK release rate (up to 30 days) was achieved using whole composites …