Age-Related Properties of Aquaponics-Derived Tilapia Skin (Oreochromis niloticus): A Structural and Compositional Study.

In the last two decades, fisheries and fish industries by-products have started to be recovered for the extraction of type I collagen because of issues related to the extraction of traditional mammalian tissues. In this work, special attention has been paid to by-products from fish bred in aquaponic plants. The valorization of aquaponic fish wastes as sources of biopolymers would make the derived materials eco-friendlier and attractive in terms of profitability and cost effectiveness. Among fish species, Nile Tilapia is the second-most farmed species in the world and its skin is commonly chosen as a collagen extraction source. However, to the best of our knowledge, no studies have been carried out to investigate, in depth, the age-related differences in fish skin with the final aim of selecting the most advantageous fish size for collagen extraction. In this work, the impact of age on the structural and compositional properties of Tilapia skin was evaluated with the aim of selecting the condition that best lends itself to the extraction of type I collagen for biomedical applications, based on the known fact that the properties of the original tissue have a significant impact on those of the final product. Performed analysis showed statistically significant age-related differences. In particular, an increase in skin thickness (+110 µm) and of wavy-like collagen fiber bundle diameter (+3 µm) besides their organization variation was observed with age. Additionally, a preferred collagen molecule orientation along two specific directions was revealed, with a higher fiber orientation degree according to age. Thermal analysis registered a shift of the endothermic peak (+1.7 °C) and an increase in the enthalpy (+3.3 J/g), while mechanical properties were found to be anisotropic, with an age-dependent brittle behavior. Water (+13%) and ash (+0.6%) contents were found to be directly proportional with age, as opposed to protein (-8%) and lipid (-10%) contents. The amino acid composition revealed a decrease in the valine, leucine, isoleucine, and threonine content and an increase in proline and hydroxyproline. Lastly, fatty acids C14:0, C15:0, C16:1, C18:2n6c, C18:3n6, C18:0, C20:3n3, and C23:0 were revealed to be upregulated, while C18:1n9c was downregulated with age.

Curing and viscoelasticity of vitrimers.

We present an experimental investigation of the curing kinetics and viscoelasticity for a number of "vitrimers" recently developed by Leibler and coworkers.1-3 Vitrimers are covalently crosslinked networks that can relax stress at elevated temperatures due to thermoreversible bond-exchange reactions. The chosen formulations are composed of diglycidyl ether of bisphenol A, commercial fatty acid mixtures and an appropriate catalyst. The effects of the catalyst and functionality of the curing agents on the kinetics of the curing reactions were systematically investigated using rheometry. The curing kinetics followed the Arrhenius law and the catalyst drastically accelerated the reactions. Time-temperature superposition was used to construct master curves of the small-strain amplitude oscillatory shear moduli over wide ranges of frequencies for the cured networks. Terminal relaxation was not reached in oscillatory experiments for temperatures up to 130 °C and creep and stress relaxation experiments were used to probe the long-time relaxation. The shift factors displayed a Williams-Landel-Ferry dependence on temperature which could be divided into two regions, one above 70 °C, where the dynamics appeared to be controlled by the catalyst, and one below, controlled by the monomeric friction and the free volume of the network. The moduli of the vitrimers obeyed the classical rubber theory well, indicating that the curing reactions proceeded to completion. Furthermore, we systematically and reproducibly observed a double relaxation behavior for the vitrimers, i.e. next to the rubbery plateau at high frequencies, the storage modulus displayed a secondary plateau at lower frequencies before reaching terminal relaxation at even lower frequencies. Interestingly, 70 °C was found to be the transition point in agreement with the shift factors. To the best of our knowledge, the double relaxation behavior has not been previously reported in experimental works and recent theories do not incorporate an explanation for this behavior. Consequently, future investigations concerning the viscoelasticity of other "vitrimer-chemistries" are important to assess if the double relaxation is a universal fingerprint for vitrimers or if it is specific to the here-investigated formulations based on commercial fatty acid mixtures.

An Overview of the Measurement of Permeability of Composite Reinforcements.

Liquid composite molding (LCM) is a class of fast and cheap processes suitable for the fabrication of large parts with good geometrical and mechanical properties. One of the main steps in an LCM process is represented by the filling stage, during which a reinforcing fiber preform is impregnated with a low-viscosity resin. Darcy's permeability is the key property for the filling stage, not usually available and depending on several factors. Permeability is also essential in computational modeling to reduce costly trial-and-error procedures during composite manufacturing. This review aims to present the most used and recent methods for permeability measurement. Several solutions, introduced to monitor resin flow within the preform and to calculate the in-plane and out-of-plane permeability, will be presented. Finally, the new trends toward reliable methods based mainly on non-invasive and possibly integrated sensors will be described.

The Role of 3D Printing in the Development of a Catalytic System for the Heterogeneous Fenton Process.

Recycling of catalysts is often performed. Additive manufacturing (AM) received increasing attention in recent years in various fields such as engineering and medicine, among others. More recently, the fabrication of three-dimensional objects used as scaffolds in heterogeneous catalysis has shown innumerable advantages, such as easier handling and waste reduction, both leading to a reduction in times and costs. In this work, the fabrication and use of 3D-printed recyclable polylactic acid (PLA) scaffolds coated with an iron oxide active catalyst for Fenton reactions applied to aromatic model molecules, is presented. These molecules are representative of a wider class of intractable organic compounds, often present in industrial wastewater. The 3D-printed PLA-coated scaffolds were also tested using an industrial wastewater, determining the chemical oxygen demand (COD). The catalyst is characterized using electron microscopy coupled to elemental analysis (SEM/EDX) and thermogravimetry, demonstrating that coating leach is very limited, and it can be easily recovered and reused many times.

Autofluorescence of Model Polyethylene Terephthalate Nanoplastics for Cell Interaction Studies.

This work contributes to fill one of the gaps regarding nanoplastic interactions with biological systems by producing polyethylene terephthalate (PET) model nanoplastics, similar to those found in the marine environment, by means of a fast top-down approach based on mechanical fragmentation. Their size distribution and morphology were characterized by laser diffraction and atomic force microscopy (AFM). Their autofluorescence was studied by spectrofluorimetry and fluorescence imaging, being a key property for the evaluation of their interaction with biota. The emission spectra of label-free nanoplastics were comparable with those of PET nanoplastics labeled with Nile red. Finally, the suitability of label-free nanoplastics for biological studies was assessed by in vitro exposure with Mytilus galloprovincialis hemolymphatic cells in a time interval up to 6 h. The nanoplastic internalization into these cells, known to be provided with phagocytic activity, was assessed by fluorescence microscopy. The obtained results underlined that the autofluorescence of the model PET nanoplastics produced in the laboratory was adequate for biological studies having the potential to overcome the disadvantages commonly associated with several fluorescent dyes, such as the tendency to also stain other organic materials different from plastics, to form aggregates due to intermolecular interactions at high concentrations with a consequent decrease in fluorescence intensity, and to dye desorption from nanoparticles. The results of the autofluorescence study provide an innovative approach for plastic risk assessment.

Production and Characterization of Polyethylene Terephthalate Nanoparticles.

Microplastic (MP) pollution represents one of the biggest environmental problems that is further exacerbated by the continuous degradation in the marine environment of MPs to nanoplastics (NPs). The most diffuse plastics in oceans are commodity polymers, mainly thermoplastics widely used for packaging, such as polyethylene terephthalate (PET). However, the huge interest in the chemical vector role of micro/nanoplastics, their fate and negative effects on the environment and human health is still under discussion and the research is still sparse due also to the difficulties of sampling MPs and NPs from the environment or producing NPs in laboratory. Moreover, the research on MPs and NPs pollution relies on the availability of engineered nanoparticles similar to those present in the marine environment for toxicological, transport and adsorption studies in biological tissues as well as for wastewater remediation studies. This work aims to develop an easy, fast and scalable procedure for the production of representative model nanoplastics from PET pellets. The proposed method, based on a simple and economic milling process, has been optimized considering the peculiarities of the polymer. The results demonstrated the reliability of the method for preparing particle suspensions for aquatic microplastic research, with evident advantages compared to the present literature procedures, such as low cost, the absence of liquid nitrogen, the short production time, the high yield of the process, stability, reproducibility and polydisperse size distribution of the produced water dispersed nanometric PET.

Out-Of-Plane Permeability Evaluation of Carbon Fiber Preforms by Ultrasonic Wave Propagation.

Out-of-plane permeability of reinforcement preforms is of crucial importance in the infusion of large and thick composite panels, but so far, there are no standard experimental methods for its determination. In this work, an experimental set-up for the measurement of unsaturated through thickness permeability based on the ultrasonic wave propagation in pulse echo mode is presented. A single ultrasonic transducer, working both as emitter and receiver of ultrasonic waves, was used to monitor the through thickness flow front during a vacuum assisted resin infusion experiment. The set-up was tested on three thick carbon fiber preforms, obtained by stacking thermal bonding of balanced or unidirectional plies either by automated fiber placement either by hand lay-up of unidirectional plies. The ultrasonic data were used to calculate unsaturated out-of-plane permeability using Darcy's law. The permeability results were compared with saturated out-of-plane permeability, determined by a traditional gravimetric method, and validated by some analytical models. The results demonstrated the feasibility and potential of the proposed set-up for permeability measurements thanks to its noninvasive character and the one-side access.

3D Printing of Polymer Waste for Improving People's Awareness about Marine Litter.

This work is aimed at proposing demonstrative actions devoted to show reprocessing and recyclability of PET originating from bottles collected from the seaside, in order to increase the consumer awareness on the importance of recycling plastics. To this purpose, collected bottles were washed, cut, grinded, extruded in the form of a thin wire adopting different cooling rates, which leads to a modulation of the crystallinity content. Once having optimized the processing parameters, the extruded wire was used to produce 3D printed samples through the fused deposition modelling (FDM). The changes in the crystalline structure due to the different processing conditions were assessed by DSC and XRD analyses, while rheological tests were performed in order to evaluate any modification in the viscosity of PET after repeated processing cycles. The reduction in thermal stability was confirmed by TGA analysis, which showed a progressive decrease in the degradation temperature as processing cycles increased. Finally, tensile tests highlighted the difference in the mechanical response due to the predominance of the crystalline or amorphous phase in the tested sample. In particular, a good mechanical behavior was found for the 3D-printed samples.

Experimental and Numerical Study of Vacuum Resin Infusion of Stiffened Carbon Fiber Reinforced Panels.

Liquid resin infusion processes are becoming attractive for aeronautic applications as an alternative to conventional autoclave-based processes. They still present several challenges, which can be faced only with an accurate simulation able to optimize the process parameters and to replace traditional time-consuming trial-and-error procedures. This paper presents an experimentally validated model to simulate the resin infusion process of an aeronautical component by accounting for the anisotropic permeability of the reinforcement and the chemophysical and rheological changes in the crosslinking resin. The input parameters of the model have been experimentally determined. The experimental work has been devoted to the study of the curing kinetics and chemorheological behavior of the thermosetting epoxy matrix and to the determination of both the in-plane and out-of-plane permeability of two carbon fiber preforms using an ultrasonic-based method, recently developed by the authors. The numerical simulation of the resin infusion process involved the modeling of the resin flow through the reinforcement, the heat exchange in the part and within the mold, and the crosslinking reaction of the resin. The time necessary to fill the component has been measured by an optical fiber-based equipment and compared with the simulation results.

Catalytic Activity of Oxidized Carbon Waste Ashes for the Crosslinking of Epoxy Resins.

In this study, two different fillers were prepared from carbon-based ashes, produced from the wooden biomass of a pyro-gasification plant, and starting from lignocellulosic waste. The first type was obtained by dry ball-milling (DBA), while the second one was prepared by oxidation in H2O2 of the dry ball-milled ashes (oDBA). The characterization of the fillers included wide-angle x-ray diffraction (WAXD), thermogravimetric, and Fourier-transform infrared spectroscopy (FTIR) analysis. The DBA and oDBA fillers were then tested as possible catalysts for the crosslinking reaction of a diglycidyl ether of bisphenol A (DGEBA) with a diamine. The cure reaction was studied by means of rheometry and differential scanning calorimetry (DSC). The oDBA filler exhibits both a higher catalytic activity on the epoxide-amine reaction than the DBA sample and improved mechanical properties and glass transition temperature. The results obtained indicate, hence, the potential improvement brought by the addition of carbon-based waste ashes, which allow both increasing the flexural properties and the glass transition temperature of the epoxy resin and reducing the curing time, acting as a catalyst for the crosslinking reaction of the epoxy resin.

A Study on exfoliation of Expanded Graphite Stacks in Candelilla Wax.

A novel, green route for pre-exfoliation of graphite based on a biodegradable polymer and high-power ultrasound is presented. Candelilla wax (CW), derived from the leaves of the candelilla plant, has been used for the first time as a natural non aqueous medium to induce the pre-exfoliation of expanded graphite (EG) under ultrasonic irradiation in an economical way. The proposed method uses also D-limonene as a natural organic solvent for reducing viscosity and increasing the affinity between the polar groups of EG and candelilla wax, thus improving the intercalation/exfoliation of EG. The quality of dispersion of the nanofiller in the natural wax matrix has been evaluated using multiple techniques. The addition of EG to wax and use of ultrasonic treatment leads to a reduced crystallinity, probably due to restrictions of the molecular movements, improved thermal stability of wax, and to an increased shear thinning exponent, which are all indicative of a high degree of EG dispersion. The ultrasonic dynamic mechanical results suggest a reduction in the cluster size and a better filler dispersion in the wax matrix promoted by polar or chemical reactions between the CW fractions and the graphite stacks, which was observed by XPS analysis. The results were compared to those obtained with paraffin, a synthetic wax, and confirmed the dispersion improvement obtained by using natural wax as a pre-exfoliating medium.

Reliability of Protective Coatings for Flexible Piezoelectric Transducers in Aqueous Environments.

Electronic devices used for marine applications suffer from several issues that can compromise their performance. In particular, water absorption and permeation can lead to the corrosion of metal parts or short-circuits. The added mass due to the absorbed water affects the inertia and durability of the devices, especially for flexible and very thin micro-systems. Furthermore, the employment of such delicate devices underwater is unavoidably subjected to the adhesion of microorganisms and formation of biofilms that limit their reliability. Thus, the demand of waterproofing solutions has increased in recent years, focusing on more conformal, flexible and insulating coatings. This work introduces an evaluation of different polymeric coatings (parylene-C, poly-dimethyl siloxane (PDMS), poly-methyl methacrylate (PMMA), and poly-(vinylidene fluoride) (PVDF)) aimed at increasing the reliability of piezoelectric flexible microdevices used for sensing water motions or for scavenging wave energy. Absorption and corrosion tests showed that Parylene-C, while susceptible to micro-cracking during prolonged oscillating cycles, exhibits the best anti-corrosive behavior. Parylene-C was then treated with oxygen plasma and UV/ozone for modifying the surface morphology in order to evaluate the biofilm formation with different surface conditions. A preliminary characterization through a laser Doppler vibrometer allowed us to detect a reduction in the biofilm mass surface density after 35 days of exposure to seawater.

Lay-Up and Consolidation of a Composite Pipe by In Situ Ultrasonic Welding of a Thermoplastic Matrix Composite Tape.

In this work, the potential of preformed thermoplastic matrix composite tapes for the manufacturing of composite pipes by filament winding assisted by in situ ultrasonic welding was evaluated. Unidirectional tapes of E-glass-reinforcedamorphous poly (ethylene terephthalate) were laid up and consolidated in a filament winding machine that was modified with a set-up enabling ultrasonic welding. The obtained composite specimens were characterized by means of morphological and dynamic mechanical analysis as well as void content evaluation, in order to correlate welding parameters to composite properties.

Effects of Blank Quality on Press-Formed PEKK/Carbon Composite Parts.

The causes of delamination and porosities during press forming of pre-consolidated flat laminates (blanks) made of carbon fiber-reinforced poly(ether ketone ketone) (PEKK) were addressed in this study. In particular, the quality of the blank laminate was investigated before and after infrared heating. The consolidation quality was evaluated by thickness measurements, non-destructive inspection (NDI), and optical microscopy. The experimental results confirmed that deconsolidation phenomena can be related to residual stresses formed during blank forming in an autoclave, then released during infrared heating (IR) of the blank, determining most of the defects in IR heated blanks. These defects, generated at the pre-heating stage, were not fully removed in the consolidation stage of the press forming process. An annealing treatment, performed on autoclave-consolidated blanks above the glass transition temperature of the matrix, was proposed to reduce the formation of defects during IR heating. The stress relaxation phenomena during annealing were modelled using a simple viscoelastic model.

Air-coupled ultrasound: a novel technique for monitoring the curing of thermosetting matrices.

A custom-made, air-coupled ultrasonic device was applied to cure monitoring of thick samples (7-10 mm) of unsaturated polyester resin at room temperature. A key point was the optimization of the experimental setup in order to propagate compression waves during the overall curing reaction by suitable placement of the noncontact transducers, placed on the same side of the test material, in the so-called pitch-catch configuration. The progress of polymerization was monitored through the variation of the time of flight of the propagating longitudinal waves. The exothermic character of the polymerization was taken into account by correcting the measured value of time of flight with that one in air, obtained by sampling the air velocity during the experiment. The air-coupled ultrasonic results were compared with those obtained from conventional contact ultrasonic measurements. The good agreement between the air-coupled ultrasonic results and those obtained by the rheological analysis demonstrated the reliability of air-coupled ultrasound in monitoring the changes of viscoelastic properties at gelation and vitrification. The position of the transducers on the same side of the sample makes this technique suitable for on-line cure monitoring during several composite manufacturing technologies.

Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins.

This article compares the catalytic activities of oxidized carbon black (oCB) and graphene oxide (eGO) samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA) with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC). Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m²/g), as oxidized by the Hummers' method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.

Development of hybrid cotton/hydrogel yarns with improved absorption properties for biomedical applications.

Hyperhidrosis, or excessive sweating, is an overlooked and potentially disabling symptom, which is often seen in social anxiety disorder. In this work an innovative advanced textile material was developed for application in the management of excessive sweating, preparing a drying yarn providing improved comfort. Hybrid cotton/hydrogel yarns were obtained by combining cotton with superabsorbent hydrogels through an optimization study focused on the achievement of the most promising product in terms of absorption properties and resistance to washings. Swelling and washing tests were performed using different hydrogels, and the effect of an additional crosslinking on the materials was also evaluated by testing different solutions containing Al(3+) and Ca(2+) ions. Scanning electron microscopy and infrared spectroscopy analyses were adopted to characterize morphology and chemical structure of the hydrogels undergoing different production processes. The biocompatibility of the hybrid fabrics was demonstrated by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide colorimetric assay (MTT) through the extract method.

Smoldering and Flame Resistant Textiles via Conformal Barrier Formation.

A durable and flexible silicone-based backcoating (halogen free) is applied to the backside of an otherwise smoldering-prone and flammable fabric. When exposed to fire, cyclic siloxanes (produced by thermal decomposition of the backcoating) diffuse through the fabric in the gas phase. The following oxidation of the cyclic siloxanes forms a highly conformal and thermally stable coating that fully embeds all individual fibers and shields them from heat and oxidation. As a result, the combustion of the fabric is prevented. This is a novel fire retardant mechanism that discloses a powerful approach towards textiles and multifunctional flexible materials with combined smoldering/flaming ignition resistance and fire-barrier properties.

A Perspective on the Prowaste Concept: Efficient Utilization of Plastic Waste through Product Design and Process Innovation.

This work is aimed to present an innovative technology for the reinforcement of beams for urban furniture, produced by in-mold extrusion of plastics from solid urban waste. This material, which is usually referred to as "recycled plastic lumber", is characterized by very poor mechanical properties, which results in high deflections under flexural loads, particularly under creep conditions. The Prowaste project, founded by the EACI (European Agency for Competitiveness and Innovation) in the framework of the Eco-Innovation measure, was finalized to develop an innovative technology for selective reinforcement of recycled plastic lumber. Selective reinforcement was carried out by the addition of pultruded glass rods in specific positions with respect to the cross section of the beam, which allowed optimizing the reinforcing efficiency. The reinforcement of the plastic lumber beams with pultruded rods was tested at industrial scale plant, at Solteco SL (Alfaro, Spain). The beams obtained, characterized by low cost and weight, were commercialized by the Spanish company. The present paper presents the most relevant results of the Prowaste project. Initially, an evaluation of the different materials candidates for the reinforcement of recycled plastic lumber is presented. Plastic lumber beams produced in the industrial plant were characterized in terms of flexural properties. The results obtained are interpreted by means of beam theory, which allows for extrapolation of the characteristic features of beams produced by different reinforcing elements. Finally, a theoretical comparison with other approaches which can be used for the reinforcement of plastic lumber is presented, highlighting that, among others, the Prowaste concept maximizes the stiffening efficiency, allowing to significantly reduce the weight of the components.

Development of semi- and grafted interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and collagen.

PURPOSE: The objective of this work was to develop composite hydrogels based on poly(ethylene glycol) diacrylate (PEGDA) and collagen (Coll), potentially useful for biomedical applications. METHODS: Semi-interpenetrating polymer networks (semi-IPNs) were obtained by photo-stabilizing aqueous solutions of PEGDA and acrylic acid (AA), in the presence of collagen. Further grafting of the collagen macromolecules to the PEGDA/poly(AA) network was achieved by means of a carbodiimide-mediated crosslinking reaction. The resulting hydrogels were characterized in terms of swelling capability, collagen content and mechanical properties. RESULTS AND CONCLUSIONS: The grafting procedure was found to significantly improve the mechanical stability of the IPN hydrogels, due to the establishment of covalent bonding between the PEGDA/poly(AA) and the collagen networks. The suitability of the composite hydrogels to be processed by means of stereolithography (SLA) was also investigated, toward creating biomimetic constructs with complex shapes, which might be useful either as platforms for tissue engineering applications or as tissue mimicking phantoms.