Rheological Changes in Bio-Based Filaments Induced by Extrusion-Based 3D Printing Process.

In this work, the authors investigated the impact of extrusion-based printing process on the structural characteristics of bio-based resins through rheological measurements. Two commercially available filaments made from unfilled and wood-filled polylactide (PLA) polymers were considered. Three-dimensional specimens were prepared by printing these filaments under various operating conditions, i.e., changing the extruder temperature and printing rate, and examined using time sweep tests. Specific cycle rheological testing was conducted on pelletized filaments to simulate temperature changes in the printing process. The rheological characteristics of unprocessed materials, in terms of storage (G') and loss (G″) moduli, were found to be slightly affected by temperature changes. For a pure polymer, the G' slope at a low frequency decreased over time, showing that the polymer chains evolved from a higher to a lower molecular weight. For wood-filled materials, the G' slope rose over the testing time, emphasizing the formation of a percolated network of structured filler within the matrix. On the other side, the rheological parameters of both materials were strongly impacted by the printing extrusion and the related conditions. At lower nozzle temperatures (200 °C), by decreasing the printing speed, the G' and G″ curves became increasingly different with respect to unprocessed resin; whereas at higher nozzle temperatures (220 °C), the influence of the printing speed was insignificant, and all curves (albeit distant from those of unprocessed matrix) mainly overlapped. Considerations on degradation kinetics of both materials during the printing process were also provided by fitting experimental data of complex viscosity with linear correlation over time.

Cellulose/Polyhydroxybutyrate (PHB) Composites as a Sustainable Bio-Based Feedstock to 3D-Printing Applications.

In this work, we have studied the potential application for 3D-printing of a polymer made from combining a biodegradable and biocompatible polymer (i.e., polyhydroxybutyrate, PHB) with natural bio-based fiber (i.e., cellulose). To this end, a masterbatch at 15 wt.% in filler content was prepared by melt-blending, and then this system was "diluted" with pure PHB in a second extrusion phase in order to produce filaments at 1.5 and 3 wt.% of cellulose. For comparison, a filament made of 100% virgin PHB pellets was prepared under the same conditions. All the systems were then processed in the 3D-printer apparatus, and specimens were mainly characterized by static (tensile and flexural testing) and dynamic mechanical analysis. Thermogravimetric analysis, differential scanning calorimetry, spectroscopic measurements, and morphological aspects of PHB polymer and composites were also discussed. The results showed a significant negative impact of the process on the mechanical properties of the basic PHB with a reduction in both tensile and flexural mechanical properties. The PHB-cellulose composites showed a good dispersion filler in the matrix but a poor interfacial adhesion between the two phases. Furthermore, the cellulose had no effect on the melting behavior and the crystallinity of the polymer. The addition of cellulose improved the thermal stability of the polymer and minimized the negative impact of extrusion. The mechanical performance of the composites was found to be higher compared to the corresponding (processed) polymer.

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.

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.

A thermoresponsive gel photoreleasing nitric oxide for potential ocular applications.

We report herein the design, preparation, characterization and biological evaluation of a thermoresponsive gel based on binary mixtures of Pluronic® co-polymers F127 and P123, the latter being covalently functionalized with a nitric oxide (NO) photodonor (NOPD). The weight ratio between the two polymeric components is optimized in order to observe gelation of their saline water solution in the range of 32-35 °C, in order to exploit the therapeutic properties of NO for potential ocular applications. Rheological measurements were performed to evaluate the gelation temperature and, hence, to select a co-polymer mixture specifically appropriate for the reference application. Integration of the NOPD into the polymeric scaffold does not affect its rheological and spectroscopic properties, making it a good absorber of visible light both in solution and in the gel phase. Irradiation of the saline solution of the polymeric components with visible light triggers NO release, which occurs with an efficiency of more than one order of magnitude faster than that observed for the isolated NOPD. The polymeric system fully preserves such photobehavior after gelation as demonstrated by the effective NO photorelease from the gel matrix and its diffusion in the supernatant upon illumination. The gel is well-tolerated in both dark and light conditions by corneal cells, while being able to induce growth inhibition towards Staphylococcus aureus under visible light irradiation and has high moduli which can contribute to an adequate retention time within the eyes.

Melt-spun bioactive sutures containing nanohybrids for local delivery of anti-inflammatory drugs.

In this work, a novel concept is introduced in drug-eluting fibres to ensure a good control of drug delivery features and wide applicability to different bioactive compounds. Composite bioactive sutures based on fibre grade poly(ε-caprolactone) (PCL) and loaded with the anti-inflammatory drug Diclofenac (Dic) or a Dic nanohybrid where the drug is intercalated in a synthetic hydrotalcite (Mg/Al hydroxycarbonate) (HT-Dic) were developed. Fibres were prepared by melt-spinning at different PCL/HT-Dic/Dic ratios and analysed in terms of morphology, mechanical properties and drug release features. Results emphasized that tensile properties of fibres are clearly affected by Dic or HT-Dic addition, while the presence of knots has limited influence on the mechanical behaviour of the sutures. Release of Dic strongly depends on how Dic is loaded in the fibre (as free or nanohybrid) whereas the combination of free Dic and HT-Dic can allow a further tuning of release profile. In vivo experiments show a reduction of inflammatory responses associated with Dic-loaded fibers. Thus, a proof of principle is provided for a novel class of bioactive sutures integrating advanced controlled-release technologies.