A novel electrical depercolation model for stretchable nanocomposite strain sensors.

Flexible strain sensors have been subject to intense research efforts in recent years, in an attempt to overcome the limitations of their rigid counterparts and find use in demanding applications. In this work, the effective calibration of resistive-type, stretchable strain sensors is discussed. A new model for the piezoresistive response of stretchable polymer nanocomposite strain sensors is presented which facilitates calibration over the full conducting strain range of the material. This offers the potential to vastly improve the practical working range of sensors made using soft conductive nanocomposites, as well as to obtain key information towards improvement of sensing performance. The model has been successfully applied to multiple experimental measurements on silicone rubber (SR) nanocomposites reinforced with reduced graphene oxide (rGO) over a range of filler loadings. The effect of parameters such as filler dimensions, filler orientation and dispersion state is discussed, while predictions on sensitivity and working range are made on the basis of interparticle distance modelling.

Multifunctional Ti3C2Tx MXene-reinforced thermoplastic starch nanocomposites for sustainable packaging solutions.

Starch-derived films exhibit significant potential for packaging applications owing to their low cost, biodegradable characteristics, and natural abundance. Nonetheless, there is a demand to enhance their mechanical properties and moisture resistance to broaden their use. In this study, high performing sorbitol-plasticized starch/Ti3C2Tx MXene nanocomposites, reinforced with ultra-low filler contents, were fabricated for the first time in literature. The MXene nanoplatelets were well-dispersed within the starch matrix while there was a tendency for the fillers to align in-plane, as revealed by polarized Raman spectroscopy. The produced nanocomposite films demonstrate remarkable effectiveness in blocking UV light, offering an additional valuable attribute in food packaging. The Young's modulus and tensile strength of starch films containing 0.75 wt% MXene increased from 439.9 and 11.0 MPa to 764.3 and 20.8 MPa, respectively. The introduction of 1 wt% MXene nanoplatelets reduced the water vapour permeability of starch films from 2.78 × 10-7 to 1.80 × 10-7 g/m h Pa due to the creation of highly tortuous paths for water molecules. Micromechanical theories were also implemented to understand further the reinforcing mechanisms in the biobased nanocomposites. The produced starch nanocomposites not only capitalize on the biodegradable and renewable nature of starch but also harness the unique properties of nanomaterials, paving the way for sustainable and high-performance packaging solutions that align with both consumer and environmental demands.

Tailored Out-of-Oven Energy Efficient Manufacturing of High-Performance Composites with Two-Stage Self-Regulating Heating via a Double Positive Temperature Coefficient Effect.

The needs for sustainable development and energy efficient manufacturing are crucial in the development of future composite materials. Out-of-oven (OoO) curing of fiber-reinforced composites based on smart conductive polymers reduces energy consumption and self-regulates the heating temperature with enhanced safety in manufacturing, presenting an excellent example of such energy efficient approaches. However, achieving the desired curing processes, especially for high-performance systems where two-stage curing is often required, remains a great challenge. In this study, a ternary system consisting of graphene nanoplatelets/HDPE/PVDF was developed, with a double positive temperature coefficient (PTC) effect achieved to fulfill stable self-regulating heating at two temperatures (120 and 150 °C). Systematic studies on both single and double PTC effects were performed, with morphological analysis to understand their pyroresistive behaviors. Compared to the oven curing process, up to 97% reduction in the energy consumption was achieved by the ternary system, while comparable thermal and mechanical properties were obtained in the carbon fiber/epoxy laminates. This work presents a new route to achieve OoO curing with two-stage self-regulating heating, which can be utilized in many high-performance composite applications.

Optimization of thermoelectric properties of carbon nanotube veils by defect engineering.

Carbon nanotubes (CNTs), with their combination of excellent electrical conductivity, Seebeck coefficient, mechanical robustness and environmental stability are highly desired as thermoelectric (TE) materials for a wide range of fields including Internet of Things, health monitoring and environmental remediation solutions. However, their high thermal conductivity (κ) is an obstacle to practical TE applications. Herein, we present a novel method to reduce the κ of CNT veils, by introducing defects, while preserving their Seebeck coefficient and electrical conductivity. Solid-state drawing of a CNT veil embedded within two polycarbonate films generates CNT veil fragments of reducing size with increasing draw ratio. A successive heat treatment, at above the polycarbonate glass-to-rubber transition temperature, spontaneously reconnects the CNT veils fragments electrically but not thermally. Stretching to a draw ratio of 1.5 and heat repairing at 170 °C leads to a dramatic 3.5-fold decrease in κ (from 46 to 13 W m-1 K-1), in contrast with a decrease in electrical conductivity of only 26% and an increase in Seebeck coefficient of 10%. To clarify the mechanism of reduction in thermal conductivity, a large-scale mesoscopic simulation of CNT veils under uniaxial stretching has also been used. This work shows that defect engineering can be a valuable strategy to optimize TE properties of CNT veils and, potentially, other thermoelectric materials.

Utilising buckling modes for the determination of the anisotropic mechanical properties of As2S3 nanosheets.

The mechanical properties and interfacial behaviour of two-dimensional (2D) materials are crucial for their use in a number of technological applications. In this paper, two buckling modes, wrinkling and buckling delamination, were used to characterize the mechanics of As2S3 nanosheets. The plane-strain moduli of As2S3 nanosheets along the armchair (AC) and zigzag (ZZ) directions were determined via periodic wrinkles to be 16.7 ± 0.5 GPa and 51.5 ± 1.9 GPa, respectively. This is one of the largest reported anisotropies of in-plane mechanical properties among 2D materials. Using the delaminated buckles, the adhesion energy of few-layer As2S3 nanosheets on silicon and polymer (polymethyl methacrylate and polydimethylsiloxane) substrates was determined to be 0.110 ± 0.006 and 0.022 ± 0.002 J m-2, respectively. A buckling mode map for As2S3 nanosheets on different substrates is presented.

Graphene Nanoplatelets as a Replacement for Carbon Black in Rubber Compounds.

In this work, we evaluated the processing and reinforcement characteristics of both carbon black (CB) and graphene nanoplatelets (GNPs) within a nitrile butadiene rubber (NBR) matrix. The aspect ratio of the GNPs was measured using atomic force microscopy (AFM) and related to the dispersion and agglomeration within the NBR matrix, as observed by scanning electron microscopy (SEM). The relationship between GNP aspect ratio and mechanical properties was studied by micromechanical modelling. The tensile and tear properties of NBR after compounding with GNPs were enhanced to a greater extent compared to carbon black, while curing times were smaller and scorch times longer, indicating some of the advantages of using GNPs. Overall, the inherent properties of GNPs along with their geometry led to the production of better-performing rubber compounds that can replace their CB-filled counterparts in applications where flexibility, tear strength and compliance are important. The influence of processing on dispersion, orientation and agglomeration of flakes was also highlighted with respect to the Young's modulus of the NBR compounds.

Self-powered ultrasensitive and highly stretchable temperature-strain sensing composite yarns.

With the emergence of stretchable/wearable devices, functions, such as sensing, energy storage/harvesting, and electrical conduction, should ideally be carried out by a single material, while retaining its ability to withstand large elastic deformations, to create compact, functionally-integrated and autonomous systems. A new class of trimodal, stretchable yarn-based transducer formed by coating commercially available Lycra® yarns with PEDOT:PSS is presented. The material developed can sense strain (first mode), and temperature (second mode) and can power itself thermoelectrically (third mode), eliminating the need for an external power-supply. The yarns were extensively characterized and obtained an ultrahigh (gauge factor ∼3.6 × 105, at 10-20% strain) and tunable (up to about 2 orders of magnitude) strain sensitivity together with a very high strain-at-break point (up to ∼1000%). These PEDOT:PSS-Lycra yarns also exhibited stable thermoelectric behavior (Seebeck coefficient of 15 µV K-1), which was exploited both for temperature sensing and self-powering (∼0.5 µW, for a 10-couple module at ΔT ∼ 95 K). The produced material has potential to be interfaced with microcontroller-based systems to create internet-enabled, internet-of-things type devices in a variety of form factors.

Progressive Phosphorylation Modulates the Self-Association of a Variably Modified Histone H3 Peptide.

Protein phosphorylation is a key regulatory mechanism in eukaryotic cells. In the intrinsically disordered histone tails, phosphorylation is often a part of combinatorial post-translational modifications and an integral part of the "histone code" that regulates gene expression. Here, we study the association between two histone H3 tail peptides modified to different degrees, using fully atomistic molecular dynamics simulations. Assuming that the initial conformations are either α-helical or fully extended, we compare the propensity of the two peptides to associate with one another when both are unmodified, one modified and the other unmodified, or both modified. The simulations lead to the identification of distinct inter- and intramolecular interactions in the peptide dimer, highlighting a prominent role of a fine-tuned phosphorylation rheostat in peptide association. Progressive phosphorylation appears to modulate peptide charge, inducing strong and specific intermolecular interactions between the monomers, which do not result in the formation of amorphous or ordered aggregates, as documented by experimental evidence derived from Circular Dichroism and NMR spectroscopy. However, upon complete saturation of positive charges by phosphate groups, this effect is reversed: intramolecular interactions prevail and dimerization of zero-charge peptides is markedly reduced. These findings underscore the role of phosphorylation thresholds in the dynamics of intrinsically disordered proteins. Phosphorylation rheostats might account for the divergent effects of histone modifications on the modulation of chromatin structure.

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends.

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated.

Tuning the Properties of Furandicarboxylic Acid-Based Polyesters with Copolymerization: A Review.

Polyesters based on 2,5-furandicarboxylic acid (FDCA) are a new class of biobased polymers with enormous interest, both from a scientific and industrial perspective. The commercialization of these polymers is imminent as the pressure for a sustainable economy grows, and extensive worldwide research currently takes place on developing cost-competitive, renewable plastics. The most prevalent method for imparting these polymers with new properties is copolymerization, as many studies have been published over the last few years. This present review aims to summarize the trends in the synthesis of FDCA-based copolymers and to investigate the effectiveness of this approach in transforming them to a more versatile class of materials that could potentially be appropriate for a number of high-end and conventional applications.

Realising biaxial reinforcement via orientation-induced anisotropic swelling in graphene-based elastomers.

The biaxial mechanical properties constitute another remarkable advantage of graphene, but their evaluation has been overlooked in polymer nanocomposites. Herein, we provided an innovative and practical method to characterise biaxial reinforcement from graphene via swelling of elastomers, where graphene nanoplatelets (GNPs) were controlled to be oriented in-plane. The in-plane-aligned graphene imposed a biaxial constraining force to the elastomer during the swelling process that led to the anisotropic swelling behaviour of the bulk nanocomposites. This unconventional swelling behaviour was successfully modelled using statistical mechanics. Novel in situ Raman band shift measurements were also performed during the de-swelling process of the samples. The characteristic 2D band shift of the GNPs, imposed by stress transfer during the de-swelling procedure, was of the order of 0.1 cm-1 per % strain, enabling the calculation of the effective biaxial Young's modulus of the GNPs in the nanocomposites (∼2 GPa). The determination of the biaxial modulus of GNPs contributed to the evaluation of their Poisson's ratio (∼0.34), which is very important but highly impractical to be measured directly on a nanoscale-sized specimen.

Mechanisms of mechanical reinforcement by graphene and carbon nanotubes in polymer nanocomposites.

Polymer nanocomposites reinforced with carbon-based nanofillers are gaining increasing interest for a number of applications due to their excellent properties. The understanding of the reinforcing mechanisms is, therefore, very important for the maximization of performance. This present review summarizes the current literature status on the mechanical properties of composites reinforced with graphene-related materials (GRMs) and carbon nanotubes (CNTs) and identifies the parameters that clearly affect the mechanical properties of the final materials. It is also shown how Raman spectroscopy can be utilized for the understanding of the stress transfer efficiency from the matrix to the reinforcement and it can even be used to map stress and strain in graphene. Importantly, it is demonstrated clearly that continuum micromechanics that was initially developed for fibre-reinforced composites is still applicable at the nanoscale for both GRMs and CNTs. Finally, current problems and future perspectives are discussed.

The strength of mechanically-exfoliated monolayer graphene deformed on a rigid polymer substrate.

The deformation and fracture behaviour of one-atom-thick mechanically exfoliated graphene has been studied in detail. Monolayer graphene flakes with different lengths, widths and shapes were successfully prepared by mechanical exfoliation and deposited onto poly(methyl methacrylate) (PMMA) beams. The fracture behaviour of the monolayer graphene was followed by deforming the PMMA beams. Through in situ Raman mapping at different strain levels, the distributions of strain over the graphene flakes were determined from the shift of the graphene Raman 2D band. The failure mechanisms of the exfoliated graphene were either by flake fracture or failure of the graphene/polymer interface. The fracture of the flakes was observed from the formation of cracks identified from the appearance of lines of zero strain in the strain contour maps. It was found that the strength of the monolayer graphene flakes decreased with increasing flake width. The strength dropped to less than ∼10 GPa for large flakes, thought to be due to the presence of defects. It is shown that a pair of topological defects in monolayer graphene will form a pseudo crack and the effect of such defects upon the strength of monolayer graphene has been modelled using molecular mechanical simulations.

Thermal Decomposition Kinetics and Mechanism of In-Situ Prepared Bio-based Poly(propylene 2,5-furan dicarboxylate)/Graphene Nanocomposites.

Bio-based polyesters are a new class of materials that are expected to replace their fossil-based homologues in the near future. In this work, poly(propylene 2,5-furandicarboxylate) (PPF) nanocomposites with graphene nanoplatelets were prepared via the in-situ melt polycondensation method. The chemical structure of the resulting polymers was confirmed by 1H-NMR spectroscopy. Thermal stability, decomposition kinetics and the decomposition mechanism of the PPF nanocomposites were studied in detail. According to thermogravimetric analysis results, graphene nanoplatelets did nοt affect the thermal stability of PPF at levels of 0.5, 1.0 and 2.5 wt.%, but caused a slight increase in the activation energy values. Pyrolysis combined with gas chromatography and mass spectroscopy revealed that the decomposition mechanism of the polymer was not altered by the presence of graphene nanoplatelets but the extent of secondary homolytic degradation reactions was increased.

Exploring Next-Generation Engineering Bioplastics: Poly(alkylene furanoate)/Poly(alkylene terephthalate) (PAF/PAT) Blends.

Polymers from renewable resources and especially strong engineering partially aromatic biobased polyesters are of special importance for the evolution of bioeconomy. The fabrication of polymer blends is a creative method for the production of tailor-made materials for advanced applications that are able to combine functionalities from both components. In this study, poly(alkylene furanoate)/poly(alkylene terephthalate) blends with different compositions were prepared by solution blending in a mixture of trifluoroacetic acid and chloroform. Three different types of blends were initially prepared, namely, poly(ethylene furanoate)/poly(ethylene terephthalate) (PEF/PET), poly(propylene furanoate)/poly(propylene terephthalate) (PPF/PPT), and poly(1,4-cyclohenedimethylene furanoate)/poly(1,4-cycloxehane terephthalate) (PCHDMF/PCHDMT). These blends' miscibility characteristics were evaluated by examining the glass transition temperature of each blend. Moreover, reactive blending was utilized for the enhancement of miscibility and dynamic homogeneity and the formation of copolymers through transesterification reactions at high temperatures. PEF⁻PET and PPF⁻PPT blends formed a copolymer at relatively low reactive blending times. Finally, poly(ethylene terephthalate-co-ethylene furanoate) (PETF) random copolymers were successfully introduced as compatibilizers for the PEF/PET immiscible blends, which resulted in enhanced miscibility.

Hydrogel matrices based on elastin and alginate for tissue engineering applications.

Hydrogels from natural polymers are widely used in tissue engineering due to their unique properties, especially when regarding the cell environment and their morphological similarity to the extracellular matrix (ECM) of native tissues. In this study, we describe the production and characterization of novel hybrid hydrogels composed of alginate blended with elastin from bovine neck ligament. The properties of elastin as a component of the native ECM were combined with the excellent chemical and mechanical stability as well as biocompatibility of alginate to produce two hybrid hydrogels geometries, namely 2D films obtained using sonication treatment and 3D microcapsules produced by pressure-driven extrusion. The resulting blend hydrogels were submitted to an extensive physico-chemical characterization. Furthermore, the biological compatibility of these materials was assessed using normal human dermal fibroblasts, indicating the suitability of this blend for soft tissue engineering.

Synthesis and Characterization of In-Situ-Prepared Nanocomposites Based on Poly(Propylene 2,5-Furan Dicarboxylate) and Aluminosilicate Clays.

Poly(propylene 2,5-furan dicarboxylate) (PPF), or poly(trimethylene 2,5-furan dicarboxylate) (PTF), is a biobased alipharomatic polyester that is expected to replace its fossil-based terephthalate (PPT) and naphthate (PPN) homologues. PPF possesses exceptional gas barrier properties, but its slow crystallization rate might affect its success in specific applications in the future. Therefore, a series of PPF based nanocomposites with the nanoclays Cloisite®-Na (MMT), Cloisite®-20A (MMT 20A), and halloysite nanotubes (HNT) were synthesized via the in situ transterification and polycondensation method. The effect of the nanoclays on the structure, thermal, and crystallization properties of PPF was studied with several methods including infrared spectroscopy (IR), Nuclear Resonance Spectroscopy (¹H-NMR), Wide Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). The insertion of the nanofillers in the polymer matrix altered the crystallization rates, and TGA results showed good thermal stability, since no significant mass loss occurred up to 300 °C. Finally, the degradation mechanism was studied in depth with Pyrolysis-Gas Chromatography/Mass Spectroscopy, and it was found that ß-scission is the dominant degradation mechanism.

Soft-matrices based on silk fibroin and alginate for tissue engineering.

Soft tissue regeneration requires the use of matrices that exhibit adequate mechanical properties as well as the ability to supply nutrients and oxygen, and to remove metabolic bio-products. In this work, we describe the development of hydrogels based on the blend between alginate (Alg) and silk fibroin (SF). Herein, we report two main strategies to combine cells with biomaterials: cells are either seeded onto prefabricated hydrogels films (2D), or encapsulated during hydrogel microcapsules formation (3D). Both geometries were successfully produced and characterized. FTIR results indicated a change of conformation of SF from random coil to ß-sheet after hydrogel formation. The thermal degradation behavior of films and microcapsules fabricated from Alg, and Alg/SF was dependent on the hydrogel composition and on the geometry of the samples. The presence of SF caused decreased water uptake ability and affected the degradation behavior. Mechanical tests showed that addition of SF promotes an increase in storage modulus, leading to a stiffer material as compared with pure Alg (6 times higher stiffness). Moreover, the in vitro cell-material interaction on Alg/SF hydrogels of different geometries was investigated using human umbilical vein endothelial cells (HUVECs). Viability, attachment, spreading and proliferation of HUVECs were significantly increased on Alg/SF hydrogels compared to neat Alg. These findings indicate that Alg/SF hydrogel is a promising material for the biomedical applications in tissue-engineering and regeneration.

Amino-Functionalized Multiwalled Carbon Nanotubes Lead to Successful Ring-Opening Polymerization of Poly(ε-caprolactone): Enhanced Interfacial Bonding and Optimized Mechanical Properties.

In this work, the synthesis, structural characteristics, interfacial bonding, and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites with small amounts (0.5, 1.0, and 2.5 wt %) of amino-functionalized multiwalled carbon nanotubes (f-MWCNTs) prepared by ring-opening polymerization (ROP) are reported. This method allows the creation of a covalent-bonding zone on the surface of nanotubes, which leads to efficient debundling and therefore satisfactory dispersion and effective load transfer in the nanocomposites. The high covalent grafting extent combined with the higher crystallinity provide the basis for a significant enhancement of the mechanical properties, which was detected in the composites with up to 1 wt % f-MWCNTs. Increasing filler concentration encourages intrinsic aggregation forces, which allow only minor grafting efficiency and poorer dispersion and hence inferior mechanical performance. f-MWCNTs also cause a significant improvement on the polymerization reaction of PCL. Indeed, the in situ polymerization kinetics studies reveal a significant decrease in the reaction temperature, by a factor of 30-40 °C, combined with accelerated the reaction kinetics during initiation and propagation and a drastically reduced effective activation energy.

Fabrication of alginate-gelatin crosslinked hydrogel microcapsules and evaluation of the microstructure and physico-chemical properties.

Microencapsulation of cells by using biodegradable hydrogels offers numerous attractive features for a variety of biomedical applications including tissue engineering. This study highlights the fabrication of microcapsules from an alginate-gelatin crosslinked hydrogel (ADA-GEL) and presents the evaluation of the physico-chemical properties of the new microcapsules which are relevant for designing suitable microcapsules for tissue engineering. Alginate di-aldehyde (ADA) was synthesized by periodate oxidation of alginate which facilitates crosslinking with gelatin through Schiff's base formation between the free amino groups of gelatin and the available aldehyde groups of ADA. Formation of Schiff's base in ADA-GEL and aldehyde groups in ADA was confirmed by FTIR and NMR spectroscopy, respectively. Thermal degradation behavior of films and microcapsules fabricated from alginate, ADA and ADA-GEL was dependent on the hydrogel composition. The gelation time of ADA-GEL was found to decrease with increasing gelatin content. The swelling ratio of ADA-GEL microcapsules of all compositions was significantly decreased, whereas the degradability was found to increase with the increase of gelatin ratio. The surface morphology of the ADA-GEL microcapsules was totally different from that of alginate and ADA microcapsules, observed by SEM. Two different buffer solutions (with and without calcium salt) have an influence on the stability of microcapsules which had a significant effect on the gelatin release profile of ADA-GEL microcapsules in these two buffer solutions.