Antibacterial and Chemical Characterization of Silica-Quercetin-PEG Hybrid Materials Synthesized by Sol-Gel Route.

This paper aims to synthesize, via the sol-gel method, a biomaterial usable in the medical field. Here, the silica-PEG-quercetin system was evaluated in relation to the different concentrations of PEG (0, 6, 12, 24, 50 wt%) and quercetin (0, 5, 10, 15 wt%), respectively. In addition, Fourier Transform-Infrared spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Kirby-Bauer analyses were performed. FT-IR was used to evaluate the hybrid formation and the influence of both PEG and Quercetin in the hybrid synthesized materials, SEM was used to evaluate the morphological properties, while the Kirby-Bauer test was used to understand the ability of the materials to inhibit the growth of the assayed bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Enterococcus faecalis, and Staphylococcus aureus).

Specific Heat Capacity and Thermal Conductivity Measurements of PLA-Based 3D-Printed Parts with Milled Carbon Fiber Reinforcement.

This research focuses on the thermal characterization of 3D-printed parts obtained via fused filament fabrication (FFF) technology, which uses a poly(lactic acid) (PLA)-based filament filled with milled carbon fibers (MCF) from pyrolysis at different percentages by weight (10, 20, 30 wt%). Differential scanning calorimetry (DSC) and thermal conductivity measurements were used to evaluate the thermal characteristics, morphological features, and heat transport behavior of the printed specimens. The experimental results showed that the addition of MCF to the PLA matrix improved the conductive properties. Scanning electron microscopy (SEM) micrographs were used to obtain further information about the porosity of the systems.

3D-Printed micro-optofluidic device for chemical fluids and cells detection.

In this work, it is presented a micro-optofluidic flow detector used for on-chip biological and chemical samples investigation. It is made in Poly-dimethyl-siloxane using a master-slave approach based on the 3D-Printing techniques. The micro-optofluidic device is made by assembling a microfluidic T-junction with a micro-optical section that consists of two optical fiber insertions and a PDMS gold-spattered micro-waveguide. The working principle in the detection is based on a different light transmission correlated to the fluid interfering with the laser beam in a micro-channel section. The proposed solution allows to realize a PDMS micro-device taking the advantage of 3D- Printing and goes beyond the restriction in the material selection. The device's performances were tested in the fluids detection and in the evaluation of the cell concentrations. Additionally, the micro-device was used as a real-time two-phase fluids flow detector. The two-phases flows were successfully monitored in different experimental conditions, varying both hydrodynamic and optical external stimuli.

Design, Preparation and Thermal Characterization of Polystyrene Composites Reinforced with Novel Three-Cages POSS Molecules.

Novel polystyrene (PS)/polyhedral oligomeric silsequioxanes (POSSs) nanocomposites were designed and prepared by in situ polymerization, using, for the first time, three-cage POSS molecules. The synthesized compounds were first characterized by Fourier transform infrared spectroscopy (FTIR) and 1H NMR spectroscopy to verify the obtaining of the designed products before their thermal performance was evaluated and compared with those of pristine PS and the corresponding single-cage POSSs nanocomposites. The thermal behaviour was checked by the means of the differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) was also used to confirm the hypothesis about the dispersion/aggregation of the POSS molecules into the polymer matrix. The parameters chosen to evaluate the thermal stability of the investigated compounds, namely temperature at 5% of mass loss (T5%) and solid residue at 700 °C, showed a significant increase in the stability of the polymers reinforced with the three-cages POSS, in comparison to both PS and single-cage POSS reinforced PSs, which therefore turn out to be promising molecular fillers for nanocomposite production.

Optimization of ZnO Nanorods Growth on Polyetheresulfone Electrospun Mats to Promote Antibacterial Properties.

Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic-polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staphylococcus aureus and Staphylococcus epidermidis) Grams. Since antimicrobial action is strictly related to the quantity of ZnO present on surface, a CBD process optimization is performed to achieve the best results in terms of coverage uniformity and reproducibility. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) provide morphological and compositional analysis of PES/ZnO mats while thermogravimetric analysis (TGA) is useful to assess the best process conditions to guarantee the higher amount of ZnO with respect to PES scaffold. Biocidal action is associated to Zn2+ ion leaching in solution, easily indicated by UV-Vis measurement of metallation of free porphyrin layers deposited on glass.

Epoxy-Based Blend Formulation for Dual Curing in Liquid Crystal Display 3D Printing: A Study on Thermomechanical Properties Variation for Enhanced Printability.

The aim of this study was to explore the thermal properties of epoxy-acrylate blends for the liquid crystal display (LCD) 3D printing technique. Starting from an epoxy-acrylate blend with a ratio of epoxy to acrylate of 50:50, the effect of adding a reactive monofunctional epoxy diluent was evaluated. The diluent was a resin composed by oxirane, mono[(C12-14 alkyl) methyl] derivatives selected for its low viscosity (i.e., 1.8 Poise) at room temperature and its reactivity. The diluent content varied from 15 to 25 wt% and, for all the formulation, double curing cycles, where thermal curing followed photocuring, were studied. The effect of different curing temperatures was also evaluated. The control of the diluent content and of the curing temperature allowed tailoring of the thermomechanical resin properties while improving the resin's processability. The glass transition ranged from 115.4 °C to 90.8 °C depending on the combination of diluent content and post-curing temperature. The resin developed displayed a faster processing time tested on a reference part with printing time of 4 h and 20 min that was much lower than the printing times (7 and 16 h) observed for the starting formulations.

3D-printed biosensors in biomedical applications exploiting plasmonic phenomena and antibody self-assembled monolayers.

In this work, a 3D-printed plasmonic chip based on a silver-gold bilayer was developed in order to enhance the optical response of the surface plasmon resonance (SPR) probe. More specifically, numerical and experimental results were obtained on the 3D-printed SPR platform based on a silver-gold bilayer. Then, the optimized probe's gold plasmonic interface was functionalized with a specific antibody directed against the p27Kip1 protein (p27), an important cell cycle regulator. The 3D-printed plasmonic biosensor was tested for p27 detection with good selectivity and a detection limit of 55 pM. The biosensor system demonstrated performance similar to commercially available ELISA (enzyme-linked immunoassay) kits, with several advantages, such as a wide detection range and a modular and simple-based architecture. The proposed biosensing technology offers flexible deployment options that are useful in disposable, low-cost, small-size, and simple-to-use biochips, envisaging future applications in experimental and biomedical research.

Chemical Recycling of Fully Recyclable Bio-Epoxy Matrices and Reuse Strategies: A Cradle-to-Cradle Approach.

Currently, the epoxy resin market is expressing concerns about epoxy resins' non-recyclability, which can hinder their widespread use. Moreover, epoxy monomers are synthesized via petroleum-based raw materials, which also limits their use. So, it is crucial to find more environmentally friendly alternative solution for their formulation. Within this context, the aim of this paper is to exploit a Cradle-to-Cradle approach, which consists of remodeling and reshaping the productive cycle of consumer products to make sure that they can be infinitely reused rather than just being recycled with a downgrading of their properties or uses, according to the principle of the complete circular economy. Indeed, after starting with a fully-recyclable bio-based epoxy formulation and assessing its recyclability as having a process yield of 99%, we obtained a recycled polymer that could be reused, mixing with the same bio-based epoxy formulation with percentages varying from 15 wt% to 27 wt%. The formulation obtained was thoroughly characterized by a dynamic-mechanical analysis, differential scanning calorimetry, and flexural tests. This approach had two advantages: (1) it represented a sustainable disposal route for the epoxy resin, with nearly all the epoxy resin recovered, and (2) the obtained recycled polymer could be used as a green component of the primary bio-based epoxy matrix. In the end, by using replicated general factorial designs (as statistical tools) combined with a proper optimization process, after carrying out a complete thermo-mechanical characterization of the developed epoxy formulations, the right percentage of recycled polymer content was selected with the aim of identifying the most performing epoxy matrix formulation in terms of its thermo-mechanical properties.

A Regression Approach to Model Refractive Index Measurements of Novel 3D Printable Photocurable Resins for Micro-Optofluidic Applications.

In this work, a quadratic polynomial regression model was developed to aid practitioners in the determination of the refractive index value of transparent 3D printable photocurable resins usable for micro-optofluidic applications. The model was experimentally determined by correlating empirical optical transmission measurements (the dependent variable) to known refractive index values (the independent variable) of photocurable materials used in optics, thus obtaining a related regression equation. In detail, a novel, simple, and cost-effective experimental setup is proposed in this study for the first time for collecting the transmission measurements of smooth 3D printed samples (roughness ranging between 0.04 and 2 µm). The model was further used to determine the unknown refractive index value of novel photocurable resins applicable in vat photopolymerization (VP) 3D printing techniques for manufacturing micro-optofluidic (MoF) devices. In the end, this study proved how knowledge of this parameter allowed us to compare and interpret collected empirical optical data from microfluidic devices made of more traditional materials, i.e., Poly(dimethylsiloxane) (PDMS), up to novel 3D printable photocurable resins suitable for biological and biomedical applications. Thus, the developed model also provides a quick method to evaluate the suitability of novel 3D printable resins for MoF device fabrication within a well-defined range of refractive index values (1.56; 1.70).

Projection Micro-Stereolithography to Manufacture a Biocompatible Micro-Optofluidic Device for Cell Concentration Monitoring.

In this work, a 3D printed biocompatible micro-optofluidic (MoF) device for two-phase flow monitoring is presented. Both an air-water bi-phase flow and a two-phase mixture composed of micrometric cells suspended on a liquid solution were successfully controlled and monitored through its use. To manufacture the MoF device, a highly innovative microprecision 3D printing technique was used named Projection Microstereolithography (PµSL) in combination with the use of a novel 3D printable photocurable resin suitable for biological and biomedical applications. The concentration monitoring of biological fluids relies on the absorption phenomenon. More precisely, the nature of the transmission of the light strictly depends on the cell concentration: the higher the cell concentration, the lower the optical acquired signal. To achieve this, the microfluidic T-junction device was designed with two micrometric slots for the optical fibers' insertion, needed to acquire the light signal. In fact, both the micro-optical and the microfluidic components were integrated within the developed device. To assess the suitability of the selected biocompatible transparent resin for optical detection relying on the selected working principle (absorption phenomenon), a comparison between a two-phase flow process detected inside a previously fully characterized micro-optofluidic device made of a nonbiocompatible high-performance resin (HTL resin) and the same made of the biocompatible one (BIO resin) was carried out. In this way, it was possible to highlight the main differences between the two different resin grades, which were further justified with proper chemical analysis of the used resins and their hydrophilic/hydrophobic nature via static water contact angle measurements. A wide experimental campaign was performed for the biocompatible device manufactured through the PµSL technique in different operative conditions, i.e., different concentrations of eukaryotic yeast cells of Saccharomyces cerevisiae (with a diameter of 5 µm) suspended on a PBS (phosphate-buffered saline) solution. The performed analyses revealed that the selected photocurable transparent biocompatible resin for the manufactured device can be used for cell concentration monitoring by using ad hoc 3D printed micro-optofluidic devices. In fact, by means of an optical detection system and using the optimized operating conditions, i.e., the optimal values of the flow rate FR=0.1 mL/min and laser input power P∈{1,3} mW, we were able to discriminate between biological fluids with different concentrations of suspended cells with a robust working ability R2=0.9874 and Radj2=0.9811.

Recovery of Waste Material from Biobags: 3D Printing Process and Thermo-Mechanical Characteristics in Comparison to Virgin and Composite Matrices.

The purpose of this study is to limit the environmental impact of packaging applications by promoting the recycling of waste products and the use of sustainable materials in additive manufacturing technology. To this end, a commercial polylactide acid (PLA)-based filament derived from waste production of bio-bags is herein considered. For reference, a filament using virgin PLA and one using a wood-based biocomposite were characterized as well. Preliminary testing involved infrared spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The effect of printing parameters (namely bed temperature, layer thickness, top surface layers, retraction speed, and distance) on the final aesthetics of 3D printed parts was verified. The results allow us to attest that the thermal properties of recycled polymer are comparable to those of virgin PLA and biocomposite. In the case of recycled polymer, after the extrusion temperature, bed temperature, and printing speed are estabilished the lowest allowable layer thickness and an appropriate choice of retraction movements are required in order to realize 3D-printed objects without morphological defects visible to the naked eyes. In the case of wood biocomposite, the printing process was complicated by frequent obstructions, and in none of the operating conditions was it possible to obtain an aesthetically satisfying piece of the chosen geometry (Lego-type bricks) Finally, mechanical testing on the 3D printed parts of each system showed that the recycled PLA behaves similarly to virgin and wood/PLA filaments.

Full Recycling and Re-Use of Bio-Based Epoxy Thermosets: Chemical and Thermomechanical Characterization of the Recycled Matrices.

High performances of thermosets deriving from their covalent intermolecular cross-link bonds result in their low recyclability hindering the full exploitation of a truly circular approach for cured thermosets. In this experimental work, the recyclability of a bio-based fully recyclable epoxy resin using a mild chemical recycling process was demonstrated. The recycled polymer obtained was fully characterized to ascertain its structure and properties. MALDI (Matrix-Assisted Laser Desorption/Ionization), GPC (Gel Permeation Chromatography) and NMR (Nuclear Magnetic Resonance) spectroscopy to determine the chemical structure of the recycled polymer were used. The thermomechanical properties of the cured virgin network and of the recycled product obtained were measured by DSC (Differential Scanning Calorimetry) and DMA (Dynamic Mechanical Analysis). Thermogravimetric analysis of the recycled polymer was also performed. The recycled polymer was transformed into a polyurethane by reacting it with an isocyanate. The synthetized polyurethane obtained therefrom was thoroughly characterized by thermogravimetric analysis. This approach proved the possibility to up-scale the recycled product making it available for novel applications exploiting its re-use.

Fused Deposition Modeling Parameter Optimization for Cost-Effective Metal Part Printing.

Metal 3D-printed parts are critical in industries such as biomedical, surgery, and prosthetics to create tailored components for patients, but the costs associated with traditional metal additive manufacturing (AM) techniques are typically prohibitive. To overcome this disadvantage, more cost-effective manufacturing processes are needed, and a good approach is to combine fused deposition modeling (FDM) with debinding-sintering processes. Furthermore, optimizing the printing parameters is required to improve material density and mechanical performance. The design of experiment (DoE) technique was used to evaluate the impact of three printing factors, namely nozzle temperature, layer thickness, and flow rate, on the tensile and bending properties of sintered 316L stainless steel in this study. Green and sintered samples were morphologically and physically characterized after printing, and the optimal printing settings were determined by statistical analysis, which included the surface response technique. The mechanical properties of the specimens increased as the flow rate and layer thickness increased and the nozzle temperature decreased. The optimized printing parameters for the ranges used in this study include 110% flow rate, 140 µm layer thickness, and 240 °C nozzle temperature, which resulted in sintered parts with a tensile strength of 513 MPa and an elongation at break of about 60%.

Fused Filament Fabrication of Alumina/Polymer Filaments for Obtaining Ceramic Parts after Debinding and Sintering Processes.

In this paper, a hybrid commercially available alumina/polymer filament was 3D printed and thermally treated (debinding and sintering) to obtain ceramic parts. Microscopic and spectroscopic analysis was used to thoroughly characterize the green and sintered parts in terms of their mesostructured, as well as their flexural properties. The sintered samples show an α alumina crystalline phase with a mean density of 3.80 g/cm3, a tensile strength of 232.6 ± 12.3 MPa, and a Vickers hardness of 21 ± 0.7 GPa. The mean thermal conductivity value at room temperature was equal to 21.52 ± 0.02 W/(mK). The values obtained through FFF production are lower than those obtained by conventional processes as the 3D-printed samples exhibited imperfect interlayer bonding and voids similar to those found in the structures of polymeric FFFs. Nonetheless, the highly filled ceramic filament is suitable for use in affordable and easy-to-operate FFF machines, as shown by the cost analysis of a real printed and sintered FFF part.

3D Printing Manufacturing of Polydimethyl-Siloxane/Zinc Oxide Micro-Optofluidic Device for Two-Phase Flows Control.

Tailored ZnO surface functionalization was performed inside a polydimethyl-siloxane (PDMS) microchannel of a micro-optofluidic device (mofd) to modulate its surface hydrophobicity to develop a method for fine tuning the fluid dynamics inside a microchannel. The wetting behavior of the surface is of particular importance if two different phases are used for system operations. Therefore, the fluid dynamic behavior of two immiscible fluids, (i) air-water and (ii) air-glycerol/water in PDMS mofds and ZnO-PDMS mofds was investigated by using different experimental conditions. The results showed that air-glycerol/water fluid was always faster than air-water flow, despite the microchannel treatment: however, in the presence of ZnO microstructures, the velocity of the air-glycerol/water fluid decreased compared with that observed for the air-water fluid. This behavior was associated with the strong ability of glycerol to create an H-bond network with the exposed surface of the zinc oxide microparticles. The results presented in this paper allow an understanding of the role of ZnO functionalization, which allows control of the microfluidic two-phase flow using different liquids that undergo different chemical interactions with the surface chemical terminations of the microchannel. This chemical approach is proposed as a control strategy that is easily adaptable for any embedded micro-device.

Rotational Rheology of Wood Flour Composites Based on Recycled Polyethylene.

In this paper, we study the effect of the addition of wood flour as a filler in a recycled polyethylene (r-PE) in view of its potential applications in 3D printing. The composites, prepared by melt mixing, are characterized with torque measurements performed during the compounding, dynamic rotational rheology, and infrared spectroscopy. Data show that the introduction of wood results in increased viscosity and in sensible viscous heating during the compounding. The r-PE appear to be stable at temperatures up to 180 °C while at higher temperatures the material shows a rheological response characterized by time-increasing viscoelastic moduli that suggests a thermal degradation governed by crosslinking reactions. The compounds (with wood loading up to 50% in wt.) also shows thermal stability at temperatures up to 180 °C. The viscoelastic behavior and the infrared spectra of the r-PE matrix suggests the presence of branches in the macromolecular structure due to the process. Although the addition of wood particles determines increased viscoelastic moduli, a solid-like viscoelastic response is not shown even for the highest wood concentrations. This behavior, due to a poor compatibility and weak interfacial adhesion between the two phases, is however promising in view of common processing technologies as extrusion or injection molding.

Fully Recyclable Bio-Based Epoxy Formulations Using Epoxidized Precursors from Waste Flour: Thermal and Mechanical Characterization.

Organic wastes represent an increasing pollution problem due to the exponential growth of their presence in the waste stream. Among these, waste flour cannot be easily reused by transforming it into high-value-added products. Another major problem is represented by epoxy-based thermosets, which have wide use but also poor recyclability. The object of the present paper is, therefore, to analyze both of these problems and come up with innovative solutions. Indeed, we propose a completely new approach, aimed at reusing the organic waste flour, by converting it into high-value epoxy-based thermosets that could be fully recycled into a reusable plastic matrix when added to the waste epoxy-based thermosets. Throughout the research activity, the organic waste was transformed into an epoxidized prepolymer, which was then mixed with a bio-based monomer cured with a cleavable ammine. The latter reactant was based on Recyclamine™ by Connora Technologies, and in this paper, we demonstrate that this original approach could work with the synthetized epoxy prepolymers derived from the waste flour. The cured epoxies were fully characterized in terms of their thermal, rheological, and flexural properties. The results obtained showed optimal recyclability of the new resin developed.

Microstructured Surface Plasmon Resonance Sensor Based on Inkjet 3D Printing Using Photocurable Resins with Tailored Refractive Index.

In this work, a novel approach to realize a plasmonic sensor is presented. The proposed optical sensor device is designed, manufactured, and experimentally tested. Two photo-curable resins are used to 3D print a surface plasmon resonance (SPR) sensor. Both numerical and experimental analyses are presented in the paper. The numerical and experimental results confirm that the 3D printed SPR sensor presents performances, in term of figure of merit (FOM), very similar to other SPR sensors made using plastic optical fibers (POFs). For the 3D printed sensor, the measured FOM is 13.6 versus 13.4 for the SPR-POF configuration. The cost analysis shows that the 3D printed SPR sensor can be manufactured at low cost (∼15 €) that is competitive with traditional sensors. The approach presented here allows to realize an innovative SPR sensor showing low-cost, 3D-printing manufacturing free design and the feasibility to be integrated with other optical devices on the same plastic planar support, thus opening undisclosed future for the optical sensor systems.

Eco-Sustainability of the Textile Production: Waste Recovery and Current Recycling in the Composites World.

This work aimed to review the recent scientific research, focused on the application of recycled fibers, taken from textile waste, in the field of composite materials to fulfill the eco-sustainability requirements of textile manufacturing, and promote actions for a circular economy. The yarns and fabric production represent one of the most polluting processes of the industrial world. The harmful environmental impact of the textile process has been described by reporting the different treatments involving the raw material and the filament fabrication, and concerning the uses of insecticides, fertilizers, and many other chemicals for improving the quality of the final products. In addition, solid textile waste constituted a further additional issue for the environmental sustainability of fabric production. Various strategies have been discussed and in part already adopted by many companies to recover waste fibers and prevent them from ending up in landfills. The alternatives of fiber recycling for composite realization have been presented by reporting several recent studies involving the uses of recycled fibers from the textile waste embedded in different matrices: thermoplastic polymer, thermosetting resins, natural constituents, and concrete in light of specific applications.

Kinetic Study of the Thermal and Thermo-Oxidative Degradations of Polystyrene Reinforced with Multiple-Cages POSS.

A comprehensive kinetics degradation study is carried out on novel multiple cages polyhedral oligomeric silsesquioxane (POSS)/polystyrene (PS) composites at 5% (w/w) of POSS to assess their thermal behavior with respect to the control PS and other similar POSS/PS systems studied in the past. The composites are synthesized by in situ polymerization of styrene in the presence of POSSs and characterized by 1H-NMR. The characteristics of thermal parameters are determined using kinetics literature methods, such as those developed by Kissinger and Flynn, Wall, and Ozawa (FWO), and discussed and compared with each other and with those obtained in the past for similar POSS/PS composites. A good improvement in the thermal stability with respect to neat polymer is found, but not with respect to those obtained in the past for polystyrene reinforced with single- or double-POSS cages. This behavior is attributed to the greater steric hindrance of the three-cages POSS compared with those of single- or double-cage POSS molecules.