Ink-Based Additive Manufacturing of a Polymer/Coal Composite: A Non-Traditional Reinforcement.

Coal, a crucial natural resource traditionally employed for generating carbon-rich materials and powering global industries, has faced escalating scrutiny due to its adverse environmental impacts outweighing its utility in the contemporary world. In response to the worldwide shift toward sustainability, the United States alone has witnessed an approximate 50% reduction in coal consumption. Nevertheless, the ample availability of coal has spurred interest in identifying alternative sustainable applications. This research delves into the feasibility of utilizing coal as a nonconventional carbon-rich reinforcement in direct ink writing (DIW)-based 3D printing techniques. Our investigation here involves a thermosetting resin serving as a matrix, incorporating pulverized coal (250 µm in size) and carbon black as the reinforcement and a viscosity modifier, respectively. The ink formulation is meticulously designed to exhibit shear-thinning behavior essential for DIW 3D printing, ensuring uniform and continuous printing. Mechanical properties are assessed through the 3D printing of ASTM standard specimens to validate the reinforcing impact. Remarkably, the study reveals that a 2 wt % coal concentration in the ink leads to a substantial improvement in both tensile and flexural properties, resulting in enhancements of 35 and 12.5%, respectively. Additionally, the research demonstrates the printability of various geometries with coal as reinforcement, opening up new possibilities for coal utilization while pursuing more sustainable manufacturing and applications.

Polyethylene terephthalate (PET) micro- and nanoplastic particles affect the mitochondrial efficiency of human brain vascular pericytes without inducing oxidative stress.

The objective of this investigation was to evaluate the influence of micro- and nanoplastic particles composed of polyethylene terephthalate (PET), a significant contributor to plastic pollution, on human brain vascular pericytes. Specifically, we delved into their impact on mitochondrial functionality, oxidative stress, and the expression of genes associated with oxidative stress, ferroptosis and mitochondrial functions. Our findings demonstrate that the exposure of a monoculture of human brain vascular pericytes to PET particles in vitro at a concentration of 50 µg/ml for a duration of 3, 6 and 10 days did not elicit oxidative stress. Notably, we observed a reduction in various aspects of mitochondrial respiration, including maximal respiration, spare respiratory capacity, and ATP production in pericytes subjected to PET particles for 3 days, with a mitochondrial function recovery at 6 and 10 days. Furthermore, there were no statistically significant alterations in mitochondrial DNA copy number, or in the expression of genes linked to oxidative stress and ferroptosis, but an increase of the expression of the gene mitochondrial transcription factor A (TFAM) was noted at 3 days exposure. These outcomes suggest that, at a concentration of 50 µg/ml, PET particles do not induce oxidative stress in human brain vascular pericytes. Instead, at 3 days exposure, PET exposure impairs mitochondrial functions, but this is recovered at 6-day exposure. This seems to indicate a potential mitochondrial hormesis response (mitohormesis) is incited, involving the gene TFAM. Further investigations are warranted to explore the stages of mitohormesis and the potential consequences of plastics on the integrity of the blood-brain barrier and intercellular interactions. This research contributes to our comprehension of the potential repercussions of nanoplastic pollution on human health and underscores the imperative need for ongoing examinations into the exposure to plastic particles.

3D Printing-Enabled Design and Manufacturing Strategies for Batteries: A Review.

Lithium-ion batteries (LIBs) have significantly impacted the daily lives, finding broad applications in various industries such as consumer electronics, electric vehicles, medical devices, aerospace, and power tools. However, they still face issues (i.e., safety due to dendrite propagation, manufacturing cost, random porosities, and basic & planar geometries) that hinder their widespread applications as the demand for LIBs rapidly increases in all sectors due to their high energy and power density values compared to other batteries. Additive manufacturing (AM) is a promising technique for creating precise and programmable structures in energy storage devices. This review first summarizes light, filament, powder, and jetting-based 3D printing methods with the status on current trends and limitations for each AM technology. The paper also delves into 3D printing-enabled electrodes (both anodes and cathodes) and solid-state electrolytes for LIBs, emphasizing the current state-of-the-art materials, manufacturing methods, and properties/performance. Additionally, the current challenges in the AM for electrochemical energy storage (EES) applications, including limited materials, low processing precision, codesign/comanufacturing concepts for complete battery printing, machine learning (ML)/artificial intelligence (AI) for processing optimization and data analysis, environmental risks, and the potential of 4D printing in advanced battery applications, are also presented.

Self-organization and dewetting kinetics in sub-10 nm diblock copolymer line/space lithography.

In this work, we investigated the self-assembly of a lamellar block copolymer (BCP) under different wetting conditions. We explored the influence of the chemical composition of under-layers and top-coats on the thin film stability, self-assembly kinetics and BCP domain orientation. Three different chemistries were chosen for these surface affinity modifiers and their composition was tuned in order to provide either neutral wetting (i.e. an out-of-plane lamellar structure), or affine wetting conditions (i.e. an in-plane lamellar structure) with respect to a sub-10 nm PS-b-PDMSB lamellar system. Using such controlled wetting configurations, the competition between the dewetting of the BCP layer and the self-organization kinetics was explored. We also evaluated the spreading parameter of the BCP films with respect to the configurations of surface-energy modifiers and demonstrated that BCP layers are intrinsically unstable to dewetting in a neutral configuration. Finally, the dewetting mechanisms were evaluated with respect to the different wetting configurations and we clearly observed that the rigidity of the top-coat is a key factor to delay BCP film instability.

Crosslinked Polyethylene (XLPE) Recycling via Foams.

Efficient recycling of crosslinked polyethylene has been challenging due to manufacturing difficulties caused by chemical crosslinking. This study focuses on simple processing via solid waste powder generation and particle fining for the subsequent crosslinked polyethylene inclusion and dispersion in rigid polyurethane foam. In addition, the concentration effects of crosslinked polyethylene in polyurethane were studied, showing a well-controlled foam microstructure with uniform pores, retained strength, better thermal degradation resistance, and, more importantly, increased thermal capabilities. Thus, the simple mechanical processing of crosslinked polyethylene and chemical urethane foaming showed the massive potential of recycling large amounts of crosslinked polyethylene in foams for broad applications in food packaging, house insulation, and sound reduction.

Dewetting Dynamics of Sheared Thin Polymer Films: An Experimental Study.

An experimental investigation is reported on the effect of shear on the bursting of molten ultrathin polymer films embedded in an immiscible matrix. By use of an optical microscope coupled with a shearing hot stage, the dewetting dynamics, i.e., the growth of dewetting holes, is monitored over time at various shear rates. It is observed that their circularity is modified by shear and that for all temperatures and thicknesses studied the growth speed of the formed holes rapidly increases with increasing shear rate. A model balancing capillary forces and viscous dissipation while taking into account shear thinning is then proposed and captures the main features of the experimental data, such as the ellipsoid shape of the holes and the faster dynamics in the direction parallel to the shear. This research will help to understand the instabilities occurring during processing of layered polymeric structures, such as multilayer coextrusion.

Double dynamic hydrogels formed by wormlike surfactant micelles and cross-linked polymer.

HYPOTHESIS: Interpenetrating networks consisting of a polymer network with dynamic cross-links and a supramolecular network allow obtaining hydrogels with significantly enhanced mechanical properties. EXPERIMENTS: Binary hydrogels composed of a dynamically cross-linked poly(vinyl alcohol) (PVA) network and a transient network of entangled highly charged mixed wormlike micelles (WLMs) of surfactants (potassium oleate and n-octyltrimethylammonium bromide) were prepared and studied by rheometry, SANS, USANS, cryo-TEM, and NMR spectroscopy. FINDINGS: Binary hydrogels show significantly enhanced rheological properties (a 3400-fold higher viscosity and 27-fold higher plateau modulus) as compared to their components taken separately. This is due to the microphase separation leading to local concentrating of PVA and WLMs providing larger number of polymer-polymer contacts for cross-linking and longer WLMs with more entanglements. Such materials are very promising for the application in many areas, ranging from enhanced oil recovery to biomedical uses.

Dual Transient Networks of Polymer and Micellar Chains: Structure and Viscoelastic Synergy.

Dual transient networks were prepared by mixing highly charged long wormlike micelles of surfactants with polysaccharide chains of hydroxypropyl guar above the entanglement concentration for each of the components. The wormlike micelles were composed of two oppositely charged surfactants potassium oleate and n-octyltrimethylammonium bromide with a large excess of anionic surfactant. The system is macroscopically homogeneous over a wide range of polymer and surfactant concentrations, which is attributed to a stabilizing effect of surfactants counterions that try to occupy as much volume as possible in order to gain in translational entropy. At the same time, by small-angle neutron scattering (SANS) combined with ultrasmall-angle neutron scattering (USANS), a microphase separation with the formation of polymer-rich and surfactant-rich domains was detected. Rheological studies in the linear viscoelastic regime revealed a synergistic 180-fold enhancement of viscosity and 65-fold increase of the longest relaxation time in comparison with the individual components. This effect was attributed to the local increase in concentration of both components trying to avoid contact with each other, which makes the micelles longer and increases the number of intermicellar and interpolymer entanglements. The enhanced rheological properties of this novel system based on industrially important polymer hold great potential for applications in personal care products, oil recovery and many other fields.

3D Printing-Enabled Nanoparticle Alignment: A Review of Mechanisms and Applications.

3D printing (additive manufacturing (AM)) has enormous potential for rapid tooling and mass production due to its design flexibility and significant reduction of the timeline from design to manufacturing. The current state-of-the-art in 3D printing focuses on material manufacturability and engineering applications. However, there still exists the bottleneck of low printing resolution and processing rates, especially when nanomaterials need tailorable orders at different scales. An interesting phenomenon is the preferential alignment of nanoparticles that enhance material properties. Therefore, this review emphasizes the landscape of nanoparticle alignment in the context of 3D printing. Herein, a brief overview of 3D printing is provided, followed by a comprehensive summary of the 3D printing-enabled nanoparticle alignment in well-established and in-house customized 3D printing mechanisms that can lead to selective deposition and preferential orientation of nanoparticles. Subsequently, it is listed that typical applications that utilized the properties of ordered nanoparticles (e.g., structural composites, heat conductors, chemo-resistive sensors, engineered surfaces, tissue scaffolds, and actuators based on structural and functional property improvement). This review's emphasis is on the particle alignment methodology and the performance of composites incorporating aligned nanoparticles. In the end, significant limitations of current 3D printing techniques are identified together with future perspectives.

Structural and Barrier Properties of Compatibilized PE/PA6 Multinanolayer Films.

The barrier performance and structural lightening of organic materials are increasingly desired and constitute a major challenge for manufacturers, particularly for transport and packaging. A promising technique which tends to emerge in recent years is that of multinanolayer coextrusion. The advantage is that it can produce multilayers made of thousands of very thin layers, leading to new properties due to crystalline morphology changes induced by confinement. This paper is focusing on the study of multinanolayered films with alternated polyethylene (PE), compatibilizer (PEgMA) and polyamide 6 (PA6) layers and made by a forced assembly coextrusion process equipped with layer multiplying elements (LME). PE/PA6 multilayer films consisting of 5 to 2049 layers (respectively 0 to 9 LME) were successfully obtained with well-organized multilayered structure. The evolution of the morphology and the microstructure of these two semi-crystalline polymers, when the thickness of each polymer layer decreases from micro-scale to nano-scale, was correlated to the water and gas transport properties of the PE/PA multilayers. The expected improvement of barrier properties was limited due to the on-edge orientation of crystals in very thin PE and PA6 layers. Despite this change of crystalline morphology, a slight improvement of the gas barrier properties was shown by comparing experimental results with permeabilities predicted on the basis of a serial model developed by considering a PE/PA6 interphase. This interphase observed by TEM images and the on-edge crystal orientation in multilayers were evidenced from mechanical properties showing an increase of the stiffness and the strength.

Elastic Properties of Polychloroprene Rubbers in Tension and Compression during Ageing.

Being able to predict the lifetime of elastomers is fundamental for many industrial applications. The evolution of both tensile and compression behavior of unfilled and filled neoprene rubbers was studied over time for different ageing conditions (70 °C, 80 °C and 90 °C). While Young's modulus increased with ageing, the bulk modulus remained almost constant, leading to a slight decrease in the Poisson's ratio with ageing, especially for the filled rubbers. This evolution of Poisson's ratio with ageing is often neglected in the literature where a constant value of 0.5 is almost always assumed. Moreover, the elongation at break decreased, all these phenomena having a similar activation energy (~80 kJ/mol) assuming an Arrhenius or pseudo-Arrhenius behavior. Using simple scaling arguments from rubber elasticity theory, it is possible to relate quantitatively Young's modulus and elongation at break for all ageing conditions, while an empirical relation can correlate Young's modulus and hardness shore A. This suggests the crosslink density evolution during ageing is the main factor that drives the mechanical properties. It is then possible to predict the lifetime of elastomers usually based on an elongation at break criterion with a simple hardness shore measurement.

Nanorheology with a Conventional Rheometer: Probing the Interfacial Properties in Compatibilized Multinanolayer Polymer Films.

Measuring the viscoelastic behavior of polymers in the vicinity of a surface or under confinement is an experimental challenge. Simple rheological tests of nanolayered films of polyethylene/polyamide 6 compatibilized in situ during the coextrusion process enabled the probing of these interfacial properties. Taking advantage of the different melting points and of the multiplication of the number of interfaces, a drastic increase of dynamic moduli was reported when increasing the interphase volume fraction in the films. A solid-like behavior for the interphase was identified. The complex viscosity of nanolayered films as a function of angular frequency was quantitatively captured for all samples using a weighted mixing law of bulk and interphase viscosities, without additional adjusting parameters, highlighting the interfacial synergy developed in nanolayered polymer films.

Polymer microlenses for quantifying cell sheet mechanics.

Mechanical interactions between individual cells and their substrate have been studied extensively over the past decade; however, understanding how these interactions change as cells interact with neighboring cells in the development of a cell sheet, or early stage tissue, is less developed. We use a recently developed experimental technique for quantifying the mechanics of confluent cell sheets. Living cells are cultured on a thin film of polystyrene [PS], which is attached to a patterned substrate of crosslinked poly(dimethyl siloxane) [PDMS] microwells. As cells attach to the substrate and begin to form a sheet, they apply sufficient contractile force to buckle the PS film over individual microwells to form a microlens array. The curvature for each microlens is measured by confocal microscopy and can be related to the strain and stress applied by the cell sheet using simple mechanical analysis for the buckling of thin films. We demonstrate that this technique can provide insight into the important materials properties and length scales that govern cell sheet responses, especially the role of stiffness of the substrate. We show that intercellular forces can lead to significantly different behaviors than the ones observed for individual cells, where focal adhesion is the relevant parameter.

Strain induced clustering in polyelectrolyte hydrogels.

Systematic large strain compression measurements have been performed on polyelectrolyte hydrogels based on modified PAA crosslinked by bifunctional thiols. For compressive strains larger than a critical value depending on polymer concentration, we observed a significant hysteresis, strain-hardening and a stress plateau during unloading. This was attributed to strain-induced ionic clustering due to electrostatic interactions that can become attractive if chains are close enough to each other. This phenomenon is dynamic and reversible but a long lifetime for the clusters has been identified. Although clustering between like-charge chains has been reported for hydrogels, it is the first time that this phenomenon is caused by deformation. This effect is potentially important as we strive to understand the behaviour of all polyelectrolyte hydrogels at large strains which are highly relevant for fracture properties.