Soybean-Based Polyol as a Substitute of Fossil-Based Polyol on the Synthesis of Thermoplastic Polyurethanes: The Effect of Its Content on Morphological and Physicochemical Properties.

Thermoplastic polyurethanes (TPUs) are remarkably versatile polymers due to the wide range of raw materials available for their synthesis, resulting in physicochemical characteristics that can be tailored according to the specific requirements of their final applications. In this study, a renewable bio-based polyol obtained from soybean oil is used for the synthesis of TPU via reactive extrusion, and the influence of the bio-based polyol on the multi-phase structure and properties of the TPU is studied. As raw materials, 4,4'-diphenylmethane (MDI), 1,4-butanediol, a fossil-based polyester polyol, and a bio-based polyol are used. The fossil-based to soybean-based polyol ratios studied are 100/0, 99/1, 95/5, 90/10, 80/20, and 50/50% by weight, respectively. The TPUs were characterized by size exclusion chromatography (SEC), gel content analysis, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), dynamic mechanical analysis (DMA), and contact angle measurements. The results reveal that incorporating the renewable polyol enhances the compatibility between the rigid and flexible segments of the TPU. However, due to its high functionality, the addition of soybean-based polyol can promote cross-linking. This phenomenon reduces the density of hydrogen bonds within the material, also reducing polarity and restricting macromolecular mobility, as corroborated by higher glass transition temperature (Tg) values. Remarkably, the addition of small amounts of the bio-based polyol (up to 5 wt.% of the total polyol content) results in high-molecular-weight TPUs with lower polarity, combined with suitable processability and mechanical properties, thus broadening the range of applications and improving their sustainability.

Biocompatible 3D-Printed Tendon/Ligament Scaffolds Based on Polylactic Acid/Graphite Nanoplatelet Composites.

Three-dimensional (3D) printing technology has become a popular tool to produce complex structures. It has great potential in the regenerative medicine field to produce customizable and reproducible scaffolds with high control of dimensions and porosity. This study was focused on the investigation of new biocompatible and biodegradable 3D-printed scaffolds with suitable mechanical properties to assist tendon and ligament regeneration. Polylactic acid (PLA) scaffolds were reinforced with 0.5 wt.% of functionalized graphite nanoplatelets decorated with silver nanoparticles ((f-EG)+Ag). The functionalization of graphene was carried out to strengthen the interface with the polymer. (f-EG)+Ag exhibited antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), an important feature for the healing process and prevention of bacterial infections. The scaffolds' structure, biodegradation, and mechanical properties were assessed to confirm their suitability for tendon and ligamentregeneration. All scaffolds exhibited surface nanoroughness created during printing, which was increased by the filler presence. The wet state dynamic mechanical analysis proved that the incorporation of reinforcement led to an increase in the storage modulus, compared with neat PLA. The cytotoxicity assays using L929 fibroblasts showed that the scaffolds were biocompatible. The PLA+[(f-EG)+Ag] scaffolds were also loaded with human tendon-derived cells and showed their capability to maintain the tenogenic commitment with an increase in the gene expression of specific tendon/ligament-related markers. The results demonstrate the potential application of these new 3D-printed nanocomposite scaffolds for tendon and ligament regeneration.

Experimental Validation of a Micro-Extrusion Set-Up with In-Line Rheometry for the Production and Monitoring of Filaments for 3D-Printing.

The main objective of this work is to validate an in-line micro-slit rheometer and a micro-extrusion line, both designed for the in-line monitoring and production of filaments for 3D printing using small amounts of material. The micro-filament extrusion line is first presented and its operational window is assessed. The throughputs ranged between 0.045 kg/h and 0.15 kg/h with a maximum 3% error and with a melt temperature control within 1 °C under the processing conditions tested for an average residence time of about 3 min. The rheological micro slit is then presented and assessed using low-density polyethylene (LDPE) and cyclic olefin copolymer (COC). The excellent matching between the in-line micro-rheological data and the data measured with off-line rotational and capillary rheometers validate the in-line micro-slit rheometer. However, it is shown that the COC does not follow the Cox-Merz rule. The COC filaments produced with the micro-extrusion line were successfully used in the 3D printing of specimens for tensile testing. The quality of both filaments (less than 6% variation in diameter along the filament's length) and printed specimens validated the whole micro-set-up, which was eventually used to deliver a rheological mapping of COC printability.

Incorporation of Argan Shell Flour in a Biobased Polypropylene Matrix for the Development of High Environmentally Friendly Composites by Injection Molding.

In this study, a new composite material is developed using a semi bio-based polypropylene (bioPP) and micronized argan shell (MAS) byproducts. To improve the interaction between the filler and the polymer matrix, a compatibilizer, PP-g-MA, is used. The samples are prepared using a co-rotating twin extruder followed by an injection molding process. The addition of the MAS filler improves the mechanical properties of the bioPP, as evidenced by an increase in tensile strength from 18.2 MPa to 20.8 MPa. The reinforcement is also observed in the thermomechanical properties, with an increased storage modulus. The thermal characterization and X-ray diffraction indicate that the addition of the filler leads to the formation of α structure crystals in the polymer matrix. However, the addition of a lignocellulosic filler also leads to an increased affinity for water. As a result, the water uptake of the composites increases, although it remains relatively low even after 14 weeks. The water contact angle is also reduced. The color of the composites changes to a color similar to wood. Overall, this study demonstrates the potential of using MAS byproducts to improve their mechanical properties. However, the increased affinity with water should be taken into account in potential applications.

Can Biomass Mastication Assist the Downstreaming of Polyhydroxyalkanoates Produced from Mixed Microbial Cultures?

Polyhydroxyalkanoates (PHAs) are natural polyesters which biodegrade in soils and oceans but have more than double the cost of comparable oil-based polymers. PHA downstreaming from its biomass represents 50% of its overall cost. Here, in an attempt to assist downstreaming, mastication of wet biomasses is tested as a new mechanical continuous biomass pretreatment with potential for industrial upscaling. Downstreaming conditions where both product recovery and purity are low due to the large amount of treated wet biomass (50% water) were targeted with the following process: extraction of 20 g in 100 mL solvent at 30 °C for 2 h, followed by 4.8 h digestion of 20 g in 0.3 M NaOH. Under the studied conditions, NaOH digestion was more effective than solvent extraction in recovering larger PHA amounts, but with less purity. A nearly 50% loss of PHA was seen during digestion after mastication. PHAs downstreamed by digestion with large amounts of impurities started to degrade at lower temperatures, but their melt elasticity was thermally stable at 170 °C. As such, these materials are attractive as fully PHA-compatible processing aids, reinforcing fillers or viscosity modifiers. On the other hand, wet biomass mastication before solvent extraction improves PHA purity and thermal stability as well as the melt rheology, which recovers the viscoelasticity measured with a PHA extracted from a dried biomass.

Tuning Thermal, Morphological, and Physicochemical Properties of Thermoplastic Polyurethanes (TPUs) by the 1,4-Butanediol (BDO)/Dipropylene Glycol (DPG) Ratio.

Thermoplastic polyurethanes (TPUs) are versatile polymers presenting a broad range of properties as a result of their countless combination of raw materials­in essence, isocyanates, polyols, and chain extenders. This study highlights the effect of two different chain extenders and their combination on the structure−property relationships of TPUs synthesized by reactive extrusion. The TPUs were obtained from 4,4-diphenylmethane diisocyanate (MDI), polyester diols, and the chain extenders 1,4-butanediol (BDO) and dipropylene glycol (DPG). The BDO/DPG ratios studied were 100/0, 75/25, 50/50, 25/75, and 0/100 wt.%. The TPUs were characterized by size exclusion chromatography (SEC), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), UV−vis spectroscopy, and physical-mechanical properties. The results indicate that DPG promotes compatibility between rigid (HS) and flexible (SS) segments of TPUs. Consequently, increasing DPG content (>75 wt.%) reduced the organization of the rigid segments and the degree of phase separation, increasing the polydispersity of the interdomain distance and the transparency in the UV−visible spectrum of the TPUs. Furthermore, increasing DPG content also reduced the amount of hydrogen bonds present in the rigid phase, reducing or extinguishing its glass transition temperature (TgHS) and melting temperature (Tm), and increasing the glass transition temperature of the flexible phase (TgSS). Therefore, increasing DPG content leads to a deterioration in mechanical properties and hydrolysis resistance.

On-Line Optical Monitoring of the Mixing Performance in Co-Rotating Twin-Screw Extruders.

The use of real-time techniques to evaluate the global mixing performance of co-rotating twin-screw extruders is well consolidated, but much less is reported on the specific contribution of individual screw zones. This work uses on-line flow turbidity and birefringence to ascertain the mixing performance of kneading blocks with different geometries. For this purpose, one of the barrel segments of the extruder was modified in order to incorporate four sampling devices and slit dies containing optical windows were attached to them. The experiments consisted in reaching steady extrusion and then adding a small amount of tracer. Upon opening each sampling device, material was laterally detoured from the local screw channel, and its turbidity and birefringence were measured by the optical detector. Residence time distribution curves (RTD) were obtained at various axial positions along three different kneading blocks and under a range of screw speeds. It is hypothesized that K, a parameter related to the area under each RTD curve, is a good indicator of dispersive mixing, whereas variance can be used to assess distributive mixing. The experimental data confirmed that these mixing indices are sensitive to changes in processing conditions, and that they translate the expected behavior of each kneading block geometry.

Optimization of Polymer Processing: A Review (Part II-Molding Technologies).

The application of optimization techniques to improve the performance of polymer processing technologies is of great practical consequence, since it may result in significant savings of materials and energy resources, assist recycling schemes and generate products with better properties. The present review aims at identifying and discussing the most important characteristics of polymer processing optimization problems in terms of the nature of the objective function, optimization algorithm, and process modelling approach that is used to evaluate the solutions and the parameters to optimize. Taking into account the research efforts developed so far, it is shown that several optimization methodologies can be applied to polymer processing with good results, without demanding important computational requirements. Furthermore, within the field of artificial intelligence, several approaches can reach significant success. The first part of this review demonstrated the advantages of the optimization approach in polymer processing, discussed some concepts on multi-objective optimization and reported the application of optimization methodologies to single and twin screw extruders, extrusion dies and calibrators. This second part focuses on injection molding, blow molding and thermoforming technologies.

Optimization of Polymer Processing: A Review (Part I-Extrusion).

Given the global economic and societal importance of the polymer industry, the continuous search for improvements in the various processing techniques is of practical primordial importance. This review evaluates the application of optimization methodologies to the main polymer processing operations. The most important characteristics related to the usage of optimization techniques, such as the nature of the objective function, the type of optimization algorithm, the modelling approach used to evaluate the solutions, and the parameters to optimize, are discussed. The aim is to identify the most important features of an optimization system for polymer processing problems and define the best procedure for each particular practical situation. For this purpose, the state of the art of the optimization methodologies usually employed is first presented, followed by an extensive review of the literature dealing with the major processing techniques, the discussion being completed by considering both the characteristics identified and the available optimization methodologies. This first part of the review focuses on extrusion, namely single and twin-screw extruders, extrusion dies, and calibrators. It is concluded that there is a set of methodologies that can be confidently applied in polymer processing with a very good performance and without the need of demanding computation requirements.

Poly(Lactic Acid)/Graphite Nanoplatelet Nanocomposite Filaments for Ligament Scaffolds.

The anterior cruciate ligament (ACL) is one of the most prone to injury in the human body. Due to its insufficient vascularization and low regenerative capacity, surgery is often required when it is ruptured. Most of the current tissue engineering (TE) strategies are based on scaffolds produced with fibers due to the natural ligament's fibrous structure. In the present work, composite filaments based on poly(L-lactic acid) (PLA) reinforced with graphite nanoplatelets (PLA+EG) as received, chemically functionalized (PLA+f-EG), or functionalized and decorated with silver nanoparticles [PLA+((f-EG)+Ag)] were produced by melt mixing, ensuring good filler dispersion. These filaments were produced with diameters of 0.25 mm and 1.75 mm for textile-engineered and 3D-printed ligament scaffolds, respectively. The resulting composite filaments are thermally stable, and the incorporation of graphite increases the stiffness of the composites and decreases the electrical resistivity, as compared to PLA. None of the filaments suffered significant degradation after 27 days. The composite filaments were processed into 3D scaffolds with finely controlled dimensions and porosity by textile-engineered and additive fabrication techniques, demonstrating their potential for ligament TE applications.

In-Line Rheo-Optical Investigation of the Dispersion of Organoclay in a Polymer Matrix during Twin-Screw Compounding.

The dispersion mechanisms in a clay-based polymer nanocomposite (CPNC) during twin-screw extrusion are studied by in-situ rheo-optical techniques, which relate the CPNC morphology with its viscosity. This methodology avoids the problems associated with post extrusion structural rearrangement. The polydimethylsiloxane (PDMS) matrix, which can be processed at ambient and low temperatures, is used to bypass any issues associated with thermal degradation. Local heating in the first part of the extruder allows testing of the usefulness of low matrix viscosity to enhance polymer intercalation before applying larger stresses for clay dispersion. The comparison of clay particle sizes measured in line with models for the kinetics of particle dispersion indicates that larger screw speeds promote the break-up of clay particles, whereas smaller screw speeds favor the erosion of the clay tactoids. Thus, different levels of clay dispersion are generated, which do not simply relate to a progressively better PDMS intercalation and higher clay exfoliation as screw speed is increased. Reducing the PDMS viscosity in the first mixing zone of the screw facilitates dispersion at lower screw speeds, but a complex interplay between stresses and residence times at larger screw speeds is observed. More importantly, the results underline that the use of larger stresses is inefficient per se in dispersing clay if sufficient time is not given for PDMS to intercalate the clay galleries and thus facilitate tactoid disruption or erosion.

Effects of Particle Size and Surface Chemistry on the Dispersion of Graphite Nanoplates in Polypropylene Composites.

Carbon nanoparticles tend to form agglomerates with considerable cohesive strength, depending on particle morphology and chemistry, thus presenting different dispersion challenges. The present work studies the dispersion of three types of graphite nanoplates (GnP) with different flake sizes and bulk densities in a polypropylene melt, using a prototype extensional mixer under comparable hydrodynamic stresses. The nanoparticles were also chemically functionalized by covalent bonding polymer molecules to their surface, and the dispersion of the functionalized GnP was studied. The effects of stress relaxation on dispersion were also analyzed. Samples were removed along the mixer length, and characterized by microscopy and dielectric spectroscopy. A lower dispersion rate was observed for GnP with larger surface area and higher bulk density. Significant re-agglomeration was observed for all materials when the deformation rate was reduced. The polypropylene-functionalized GnP, characterized by increased compatibility with the polymer matrix, showed similar dispersion effects, albeit presenting slightly higher dispersion levels. All the composites exhibit dielectric behavior, however, the alternate current (AC) conductivity is systematically higher for the composites with larger flake GnP.

Electrically Conductive Polyetheretherketone Nanocomposite Filaments: From Production to Fused Deposition Modeling.

The present work reports the production and characterization of polyetheretherketone (PEEK) nanocomposite filaments incorporating carbon nanotubes (CNT) and graphite nanoplates (GnP), electrically conductive and suitable for fused deposition modeling (FDM) processing. The nanocomposites were manufactured by melt mixing and those presenting electrical conductivity near 10 S/m were selected for the production of filaments for FDM. The extruded filaments were characterized for mechanical and thermal conductivity, polymer crystallinity, thermal relaxation, nanoparticle dispersion, thermoelectric effect, and coefficient of friction. They presented electrical conductivity in the range of 1.5 to 13.1 S/m, as well as good mechanical performance and higher thermal conductivity compared to PEEK. The addition of GnP improved the composites' melt processability, maintained the electrical conductivity at target level, and reduced the coefficient of friction by up to 60%. Finally, three-dimensional (3D) printed test specimens were produced, showing a Young's modulus and ultimate tensile strength comparable to those of the filaments, but a lower strain at break and electrical conductivity. This was attributed to the presence of large voids in the part, revealing the need for 3D printing parameter optimization. Finally, filament production was up-scaled to kilogram scale maintaining the properties of the research-scale filaments.

The influence of the dispersion method on the electrical properties of vapor-grown carbon nanofiber/epoxy composites.

The influence of the dispersion of vapor-grown carbon nanofibers (VGCNF) on the electrical properties of VGCNF/Epoxy composites has been studied. A homogenous dispersion of the VGCNF does not imply better electrical properties. In fact, it is demonstrated that the most simple of the tested dispersion methods results in higher conductivity, since the presence of well-distributed nanofiber clusters appears to be a key factor for increasing composite conductivity.PACS: 72.80.Tm; 73.63.Fg; 81.05.Qk.

Melt processing of chitosan-based fibers and fiber-mesh scaffolds for the engineering of connective tissues.

We report the production of chitosan-based fibers and chitosan fiber-mesh structures by melt processing (solvent-free) to be used as tissue-engineering scaffolds. The melt-based approach used to produce the scaffolds does not change their main characteristics, including the surface roughness and microporosity. The porosity, pore size, interconnectivity and mechanical performance of the scaffolds are all within the range required for various tissue-engineering applications. Biological assessments are performed in direct-contact assays. Cells are able to colonize the scaffold, including the inner porous structure. The cells show high indices of viability in all of the scaffold types.