Playing with Low Amounts of Expanded Graphite for Melt-Processed Polyamide and Copolyester Nanocomposites to Achieve Control of Mechanical, Tribological, Thermal and Dielectric Properties.

Polyamide 11 (PA11) and copolyester (TPC-E) were compounded through melt extrusion with low levels (below 10%) of expanded graphite (EG), aiming at the manufacturing of a thermally and electrically conductive composite resistant to friction and with acceptable mechanical properties. Thermal characterisation showed that the EG presence had no influence on the onset degradation temperature or melting temperature. While the specific density of the produced composite materials increased linearly with increasing levels of EG, the tensile modulus and flexural modulus showed a significant increase already at the introduction of 1 wt% EG. However, the elongation at break decreased significantly for higher loadings, which is typical for composite materials. We observed the increase in the dielectric and thermal conductivity, and the dissipated power displayed a much larger increase where high frequencies (e.g., 10 GHz) were taken into account. The tribological results showed significant changes at 4 wt% for the PA11 composite and 6 wt% for the TPC-E composite. Morphological analysis of the wear surfaces indicated that the main wear mechanism changed from abrasive wear to adhesive wear, which contributes to the enhanced wear resistance of the developed materials. Overall, we manufactured new composite materials with enhanced dielectric properties and superior wear resistance while maintaining good processability, specifically upon using 4-6 wt% of EG.

Designing Prepregnation and Fused Filament Fabrication Parameters for Recycled PP- and PA-Based Continuous Carbon Fiber Composites.

Continuous carbon fiber (cCF)-based 3D-printed polymer composites are known for their excellent flexural properties; however, the optimization of the overall process is still desired, depending on the material types involved. Here, the improved manufacturing of cCF-based composites is reported, considering virgin polyamide (PA) and postindustrial waste polypropylene (PP), and the parameters affecting the material properties are evaluated. Firstly, the prepregnation technique was optimized to manufacture cCF polymer filaments with various fiber-to-polymer ratios. Secondly, the fused filament fabrication (FFF) technique was optimized. It was observed that the layer height needs to be sufficiently low for proper interlayer adhesion. The influence of the printing temperature is more complicated, with filaments characterized by a lower fiber-to-polymer ratio requiring a higher nozzle diameter and higher temperatures for efficient printing; and for lower diameters, the best flexural properties are observed for parts printed at lower temperatures, maintaining a high interspace distance. Plasma treatment of the cCF was also explored, as was annealing of the produced parts to enhance the flexural properties, the latter being specifically interesting for the PP-based composite due to a lower wetting caused by a higher viscosity, despite supportive interfacial interactions. Eventually, overall guidelines were formulated for the successful production of cCF-based composites.

Carbon Nitride Grafting Modification of Poly(lactic acid) to Maximize UV Protection and Mechanical Properties for Packaging Applications.

Due to their biobased nature and biodegradability, poly(lactic acid) (PLA) rich blends are promising for processing in the packaging industry. However, pure PLA is brittle and UV transparent, which limits its application, so the exploration of nanocomposites with improved interfacial interactions and UV absorbing properties is worthwhile. We therefore developed and optimized synthesis routes for well-designed nanocomposites based on a PLA matrix and graphitic carbon nitride (g-C3N4; CN) nanofillers. To enhance the interfacial interaction with the PLA matrix, a silane-coupling agent (γ-methacryloxypropyl trimethoxysilane, KH570) is chemically grafted onto the CN surface after controlled oxidation with nitric acid and hydrogen peroxide. Interestingly, only 1 wt % of CNO-KH570, as synthesized under mild conditions, is needed to significantly improve the UV absorption, blocking even a large part of both UV-C, UV-B, and UV-A outperforming the UV absorption performance of PLA and, for instance, polyethylene terephthalate (PET). The low nanofiller loading of 1 wt % also results in a higher ductility with an increase in elongation at break (+73%), maintaining the tensile modulus. The results on a joint optimization of UV protection and mechanical properties are supported by a broad range of experimental characterizations, including FTIR, XRD, DSC, DSEM, FETEM, XPS, FTIR, TGA, and BET N2 adsorption-desorption analysis.

Solvent electrospinning amorphous solid dispersions with high itraconazole, celecoxib, mebendazole and fenofibrate drug loading and release potential.

In this work, the feasibility of ultra-high drug loaded amorphous solid dispersions (ASDs) for the poorly soluble itraconazole, mebendazole and celecoxib via solvent electrospinning in combination with poly(2-ethyl-2-oxazoline) and fenofibrate in combination with polyvinylpyrrolidone is demonstrated. By lowering the polymer concentration in the electrospinning solution below its individual spinnable limit, ASDs with a drug content of up to 80 wt% are obtained. This is attributed to drug-polymer interactions not being limited by default to hydrogen bonds, as also Van der Waals interactions can result in high drug loadings. The theoretically predicted miscibility by the Flory-Huggins theory is corroborated by the experimental findings based on (modulated) differential scanning calorimetry and x-ray diffraction. Globally, the maximally obtained amorphous drug loadings are higher compared to the loadings found in literature. Additionally, non-sink dissolution tests demonstrate an increase in solubility of up to 50 times compared to their crystalline counterparts. Moreover, due to the lack of precipitation biocompatible PEtOx succeeds in stabilizing the dissolved drug and inhibiting its instant precipitation. The current work thus demonstrates the broader applicability of the electrospinning technique for the production of physically stable ASDs with ultra-high drug loadings, a result which has been validated for several Biopharmaceutics Classification System class II drugs.

Multicomponent Acrylic Formulation Design for Corrosion Casting with Controlled Mechanical Properties.

Corrosion casting based on the curing of acrylic resins enables one to create casts as replicas of body systems, enhancing our knowledge of veterinary medicine. The identification of the optimal chemical formulations as well as the processing conditions, the delivery of good control during the liquid state and the excellent macroscopic properties during solidification and after use are remaining challenges. In the present work, based on the identification of more qualitative trends, it is demonstrated that multicomponent comonomer mixtures are interesting materials that can be used to expand the range of mechanical properties and can specifically result in a better balance between stiffness and flexibility while guaranteeing dimensional stability. Emphasis is put on a large pool of formulations in the testing phase to then perform a detailed mechanical flexural analysis for the most promising cases during a more rigorous testing phase, accounting for a new pragmatic protocol for the pot life. This protocol consists of a vial-based turning test and a measurement of the viscosity variation up to 1000 mPa∙s and highlights the complex interplay between the overall initial concentrations and the impact of the absence of mixing once the system is at rest. It is demonstrated that the use of only low-molar-mass crosslinkers should be avoided, and overall, an intermediate amount of crosslinkers is recommendable.

Molecular Pathways for Polymer Degradation during Conventional Processing, Additive Manufacturing, and Mechanical Recycling.

The assessment of the extent of degradation of polymer molecules during processing via conventional (e.g., extrusion and injection molding) and emerging (e.g., additive manufacturing; AM) techniques is important for both the final polymer material performance with respect to technical specifications and the material circularity. In this contribution, the most relevant (thermal, thermo-mechanical, thermal-oxidative, hydrolysis) degradation mechanisms of polymer materials during processing are discussed, addressing conventional extrusion-based manufacturing, including mechanical recycling, and AM. An overview is given of the most important experimental characterization techniques, and it is explained how these can be connected with modeling tools. Case studies are incorporated, dealing with polyesters, styrene-based materials, and polyolefins, as well as the typical AM polymers. Guidelines are formulated in view of a better molecular scale driven degradation control.

Toward More Universal Prediction of Polymer Solution Viscosity for Solvent-Based Recycling.

The viscosity of polymer solutions is important for both polymer synthesis and recycling. Polymerization reactions can become hampered by diffusional limitations once a viscosity threshold is reached, and viscous solutions complicate the cleaning steps during the dissolution-precipitation technique. Available experimental data is limited, which is more severe for green solvents, justifying dedicated viscosity data recording and interpretation. In this work, a systematic study is therefore performed on the viscosity of polystyrene solutions, considering different concentrations, temperatures, and conventional and green solvents. The results show that for the shear rate range of 1-1000 s-1, the solutions with concentrations between 5 and 39 wt % display mainly Newtonian behavior, which is further confirmed by the applicability of the segment-based Eyring-NRTL and Eyring-mNRF models. Moreover, multivariate data analysis successfully predicts the viscosity of polystyrene solutions under different conditions. This approach will facilitate future data recording for other polymer-solvent combinations while minimizing experimental effort.

Principles and Guidelines for In-Line Viscometry in Cereal Extrusion.

In the food industry, extrusion cooking finds numerous applications thanks to its high productivity and nutrient retention. More specifically, cereal extrusion, e.g., for savory snacks and breakfast products has an important market share. For such applications, rheology, which addresses viscous and elastic contributions, plays an important role in developing, optimizing, and controlling the extrusion manufacturing technique. In this context, conventional off-line rheometers are not ideal for providing data, as the goal is to replicate the exact thermomechanical history to which the food is subjected in the extrusion process. Hence, to achieve reliable analyses, in-line viscometers that have mostly been tested using oil-based polymers were introduced. Biopolymers (e.g., starch), however, are highly sensitive to both heat and mechanical degradation, and the viscometer design has to be adapted accordingly to produce an accurate measurement. Alongside a discussion of the different designs available, this review will address the most common methodologies for measuring the steady shear viscosity, extensional viscosity, and the first normal stress difference for food applications, providing researchers in the biopolymer and food engineering fields with a general introduction to this emerging topic.

Setting the Optimal Laser Power for Sustainable Powder Bed Fusion Processing of Elastomeric Polyesters: A Combined Experimental and Theoretical Study.

Additive manufacturing (AM) of polymeric materials offers many benefits, from rapid prototyping to the production of end-use material parts. Powder bed fusion (PBF), more specifically selective laser sintering (SLS), is a very promising AM technology. However, up until now, most SLS research has been directed toward polyamide powders. In addition, only basic models have been put forward that are less directed to the identification of the most suited operating conditions in a sustainable production context. In the present combined experimental and theoretical study, the impacts of several SLS processing parameters (e.g., laser power, part bed temperature, and layer thickness) are investigated for a thermoplastic elastomer polyester by means of colorimetric, morphological, physical, and mechanical analysis of the printed parts. It is shown that an optimal SLS processing window exists in which the printed polyester material presents a higher density and better mechanical properties as well as a low yellowing index, specifically upon using a laser power of 17-20 W. It is further highlighted that the current models are not accurate enough at predicting the laser power at which thermal degradation occurs. Updated and more fundamental equations are therefore proposed, and guidelines are formulated to better assess the laser power for degradation and the maximal temperature achieved during sintering. This is performed by employing the reflection and absorbance of the laser light and taking into account the particle size distribution of the powder material.

Response-Surface-Methodology-Based Increasing of the Isotropic Thermal Conductivity of Polyethylene Composites Containing Multiple Fillers.

To optimize the thermal conductivity of high-density polyethylene, 15 hybrid filler composites containing either aluminum oxide, graphite, expanded graphite, carbon nanotubes or a combination of the former, have been studied using an extrusion-compression processing tandem. The experimental density of the cube-shaped specimens is substantially lower than the theoretical density calculated by the linear mixing rule, mainly for the composites with high filler contents. The morphology of the composites, as studied by scanning electron microscopy (SEM), highlighted a good dispersion quality and random orientation of the fillers in the test specimens but also revealed air inclusions in the composites, explaining the density results. It is shown that the addition of filler(s) increases both the melt viscosity (up to ca. 270%) and the thermal conductivity (up to ca. 1000%). Hence, a very strong increase of TC can be practically hampered by a too high viscosity to enable processing. Supported by ANOVA analysis, the application of response surface methodology (RSM), assuming a perfect compression, indicates that all fillers have a significant effect on the thermal conductivity and synergistic effects can be achieved. The regression model obtained can adequately predict the thermal conductivity of composites of various compositions, as already confirmed based on three validation experiments in the present work.

Combining Chromatographic, Rheological, and Mechanical Analysis to Study the Manufacturing Potential of Acrylic Blends into Polyacrylic Casts.

Polyacrylics have been considered for a broad range of material applications, including coatings, dental applications, and adhesives. In this experimental study, the casting potential of a group of (co)monomers belonging to the acrylic family has been explored to enable a more sustainable use of these polymer materials in the medical and veterinary science field. The individual contributions of each comonomer have been analyzed, the reaction conversion has been studied via gas chromatography (GC), the rheological behavior has been characterized via stress-controlled measurements, and the final mechanical properties have been obtained from tensile, flexure, and impact tests. The GC results allow assessing the pot life and thus the working window of the casting process. For the rheological measurements, which start from low-viscous mixtures, a novel protocol has been introduced to obtain accurate absolute data. The rheological data reflect the time dependencies of the GC data but facilitate a more direct link with the macroscopic material data. Specifically, the steep increase in the viscosity with increasing reaction time for the methyl methacrylate (MMA)/ethylene glycol dimethyl methacrylate (EGDMA) case (2% crosslinker) allows maximizing several mechanical properties: the tensile/flexure modulus, the tensile/flexure stress at break, and the impact strength. This opens the pathway to more dedicated chemistry design for corrosion casting and polyacrylic material design in general.

A Combined Experimental and Modeling Study for Pellet-Fed Extrusion-Based Additive Manufacturing to Evaluate the Impact of the Melting Efficiency.

To improve the product quality of polymeric parts realized through extrusion-based additive manufacturing (EAM) utilizing pellets, a good control of the melting is required. In the present work, we demonstrate the strength of a previously developed melt removal using a drag framework to support such improvement. This model, downscaled from conventional extrusion, is successfully validated for pellet-based EAM-hence, micro-extrusion-employing three material types with different measured rheological behavior, i.e., acrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) and styrene-ethylene-butylene-styrene polymer (SEBS). The model's validation is made possible by conducting for the first time dedicated EAM screw-freezing experiments combined with appropriate image/data analysis and inputting rheological data. It is showcased that the (overall) processing temperature is crucial to enable similar melting efficiencies. The melting mechanism can vary with the material type. For ABS, an initially large contribution of viscous heat dissipation is observed, while for PLA and SEBS thermal conduction is always more relevant. It is highlighted based on scanning electron microscopy (SEM) analysis that upon properly tuning the finalization of the melting point within the envisaged melting zone, better final material properties are achieved. The model can be further used to find an optimal balance between processing time (e.g., by variation of the screw frequency) and material product performance (e.g., strength of the printed polymeric part).

Connecting Gas-Phase Computational Chemistry to Condensed Phase Kinetic Modeling: The State-of-the-Art.

In recent decades, quantum chemical calculations (QCC) have increased in accuracy, not only providing the ranking of chemical reactivities and energy barriers (e.g., for optimal selectivities) but also delivering more reliable equilibrium and (intrinsic/chemical) rate coefficients. This increased reliability of kinetic parameters is relevant to support the predictive character of kinetic modeling studies that are addressing actual concentration changes during chemical processes, taking into account competitive reactions and mixing heterogeneities. In the present contribution, guidelines are formulated on how to bridge the fields of computational chemistry and chemical kinetics. It is explained how condensed phase systems can be described based on conventional gas phase computational chemistry calculations. Case studies are included on polymerization kinetics, considering free and controlled radical polymerization, ionic polymerization, and polymer degradation. It is also illustrated how QCC can be directly linked to material properties.

Going Beyond the Carothers, Flory and Stockmayer Equation by Including Cyclization Reactions and Mobility Constraints.

A challenge in the field of polymer network synthesis by a step-growth mechanism is the quantification of the relative importance of inter- vs. intramolecular reactions. Here we use a matrix-based kinetic Monte Carlo (kMC) framework to demonstrate that the variation of the chain length distribution and its averages (e.g., number average chain length xn), are largely affected by intramolecular reactions, as mostly ignored in theoretical studies. We showcase that a conventional approach based on equations derived by Carothers, Flory and Stockmayer, assuming constant reactivities and ignoring intramolecular reactions, is very approximate, and the use of asymptotic limits is biased. Intramolecular reactions stretch the functional group (FG) conversion range and reduce the average chain lengths. In the likely case of restricted mobilities due to diffusional limitations because of a viscosity increase during polymerization, a complex xn profile with possible plateau formation may arise. The joint consideration of stoichiometric and non-stoichiometric conditions allows the validation of hypotheses for both the intrinsic and apparent reactivities of inter- and intramolecular reactions. The kMC framework is also utilized for reverse engineering purposes, aiming at the identification of advanced (pseudo-)analytical equations, dimensionless numbers and mechanistic insights. We highlight that assuming average molecules by equally distributing A and B FGs is unsuited, and the number of AB intramolecular combinations is affected by the number of monomer units in the molecules, specifically at high FG conversions. In the absence of mobility constraints, dimensionless numbers can be considered to map the time variation of the fraction of intramolecular reactions, but still, a complex solution results, making a kMC approach overall most elegant.

State-Of-The-Art Quantification of Polymer Solution Viscosity for Plastic Waste Recycling.

Solvent-based recycling is a promising approach for closed-loop recovery of plastic-containing waste. It avoids the energy cost to depolymerize the plastic but still allows to clean the polymer of contaminants and additives. However, viscosity plays an important role in handling the polymer solutions at high concentrations and in the cleaning steps. This Review addresses the viscosity behavior of polymer solutions, available data, and (mostly algebraic) models developed. The non-Newtonian viscosity models, such as the Carreau and Yasuda-Cohen-Armstrong models, pragmatically describe the viscosity of polymer solutions at different concentrations and shear rate ranges. This Review also describes how viscosity influences filtration and centrifugation processes, which are crucial steps in the cleaning of the polymer and includes a polystyrene/styrene case study.

Computational prediction of the molecular configuration of three-dimensional network polymers.

The three-dimensional arrangement of natural and synthetic network materials determines their application range. Control over the real-time incorporation of each building block and functional group is desired to regulate the macroscopic properties of the material from the molecular level onwards. Here we report an approach combining kinetic Monte Carlo and molecular dynamics simulations that chemically and physically predicts the interactions between building blocks in time and in space for the entire formation process of three-dimensional networks. This framework takes into account variations in inter- and intramolecular chemical reactivity, diffusivity, segmental compositions, branch/network point locations and defects. From the kinetic and three-dimensional structural information gathered, we construct structure-property relationships based on molecular descriptors such as pore size or dangling chain distribution and differentiate ideal from non-ideal structural elements. We validate such relationships by synthesizing organosilica, epoxy-amine and Diels-Alder networks with tailored properties and functions, further demonstrating the broad applicability of the platform.

The Transferability and Design of Commercial Printer Settings in PLA/PBAT Fused Filament Fabrication.

In many fused filament fabrication (FFF) processes, commercial printers are used, but rarely are printer settings transferred from one commercial printer to the other to give similar final tensile part performance. Here, we report such translation going from the Felix 3.0 to Prusa i3 MK3 printer by adjusting the flow rate and overlap of strands, utilizing an in-house developed blend of polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT). We perform a sensitivity analysis for the Prusa printer, covering variations in nozzle temperature, nozzle diameter, layer thickness, and printing speed (Tnozzle, dnozzle, LT, and vprint), aiming at minimizing anisotropy and improving interlayer bonding. Higher mass, larger width, and thickness are obtained with larger dnozzle, lower vprint, higher LT, and higher Tnozzle. A higher vprint results in less tensile strain at break, but it remains at a high strain value for samples printed with dnozzle equal to 0.5 mm. vprint has no significant effect on the tensile modulus and tensile and impact strength of the samples. If LT is fixed, an increased dnozzle is beneficial for the tensile strength, ductility, and impact strength of the printed sample due to better bonding from a wider raster structure, while an increased LT leads to deterioration of mechanical properties. If the ratio dnozzle/LT is greater than 2, a good tensile performance is obtained. An improved Tnozzle leads to a sufficient flow of material, contributing to the performance of the printed device. The considerations brought forward result in a deeper understanding of the FFF process and offer guidance about parameter selection. The optimal dnozzle/vprint/LT/Tnozzle combination is 0.5 mm/120 mm s-1/0.15 mm/230 °C.

Progress in Reaction Mechanisms and Reactor Technologies for Thermochemical Recycling of Poly(methyl methacrylate).

Chemical or feedstock recycling of poly(methyl methacrylate) (PMMA) by thermal degradation is an important societal challenge to enable polymer circularity. The annual PMMA world production capacity is over 2.4 × 106 tons, but currently only 3.0 × 104 tons are collected and recycled in Europe each year. Despite the rather simple chemical structure of MMA, a debate still exists on the possible PMMA degradation mechanisms and only basic batch and continuous reactor technologies have been developed, without significant knowledge of the decomposition chemistry or the multiphase nature of the reaction mixture. It is demonstrated in this review that it is essential to link PMMA thermochemical recycling with the PMMA synthesis as certain structural defects from the synthesis step are affecting the nature and relevance of the subsequent degradation reaction mechanisms. Here, random fission plays a key role, specifically for PMMA made by anionic polymerization. It is further highlighted that kinetic modeling tools are useful to further unravel the dominant PMMA degradation mechanisms. A novel distinction is made between global conversion or average chain length models, on the one hand, and elementary reaction step-based models on the other hand. It is put forward that only by the dedicated development of the latter models, the temporal evolution of degradation product spectra under specific chemical recycling conditions will become possible, making reactor design no longer an art but a science.

The Competition of Termination and Shielding to Evaluate the Success of Surface-Initiated Reversible Deactivation Radical Polymerization.

One of the challenges for brush synthesis for advanced bioinspired applications using surface-initiated reversible deactivation radical polymerization (SI-RDRP) is the understanding of the relevance of confinement on the reaction probabilities and specifically the role of termination reactions. The present work puts forward a new matrix-based kinetic Monte Carlo platform with an implicit reaction scheme capable of evaluating the growth pattern of individual free and tethered chains in three-dimensional format during SI-RDRP. For illustration purposes, emphasis is on normal SI-atom transfer radical polymerization, introducing concepts such as the apparent livingness and the molecular height distribution (MHD). The former is determined based on the combination of the disturbing impact of termination (related to conventional livingness) and shielding of deactivated species (additional correction due to hindrance), and the latter allows structure-property relationships to be identified, starting at the molecular level in view of future brush characterization. It is shown that under well-defined SI-RDRP conditions the contribution of (shorter) hindered dormant chains is relevant and more pronounced for higher average initiator coverages, despite the fraction of dead chains being less. A dominance of surface-solution termination is also put forward, considering two extreme diffusion modes, i.e., translational and segmental. With the translational mode termination is largely suppressed and the living limit is mimicked, whereas with the segmental mode termination occurs more and the termination front moves upward alongside the polymer layer growth. In any case, bimodalities are established for the tethered chains both on the level of the chain length distribution and the MHD.

Influence of Different Stabilization Systems and Multiple Ultraviolet A (UVA) Aging/Recycling Steps on Physicochemical, Mechanical, Colorimetric, and Thermal-Oxidative Properties of ABS.

Commercially mass-polymerized acrylonitrile-butadiene-styrene (ABS) polymers, pristine or modified by stabilization systems, have been injection molded and repeatedly exposed to ultravilolet A (UVA) radiation, mechanical recycling, and extra injection molding steps to study the impact of such treatments on the physicochemical, mechanical, colorimetric, and thermal-oxidative characteristics. The work focus on mimicking the effect of solar radiation behind a window glass as relevant during the lifetime of ABS polymers incorporated in electrical and electronic equipment, and interior automotive parts by using UVA technique. The accelerated aging promotes degradation and embrittlement of the surface exposed to radiation and causes physical aging, deteriorating mechanical properties, with an expressive reduction of impact strength (unnotched: up to 900%; notched: up to 250%) and strain at break (>1000%), as well as an increase in the yellowing index (e.g., 600%). UV-exposition promotes a slight increase in the tensile modulus (e.g., 10%). The addition of antioxidants (AOs) leads to a limited stabilization during the first UVA aging, although the proper AO formulation increases the thermal-oxidative resistance during all the cycles. Mechanical recycling promotes an increase in strain at break and unnotched impact strength alongside a slight decrease in tensile modulus, due to disruption of the brittle surface and elimination of the physical aging.