Intelligent process monitoring of smart polymer composites using large area graphene coated fabric sensor.

Herein, we report the development of an online process monitoring system for vacuum-assisted resin transfer molding (VARTM) process using large area graphene coated in-situ fabric sensor. Besides imparting excellent mechanical properties to the final composites, these sensors provide critical information during the composite processing including detecting defects and evaluating processing parameters. The obtained information can be used to create a digital passport of the manufacturing phase to develop a cost-effective production technique and fabricate high-quality composites.  The fabric sensor was produced using a scalable dip-coating process by coating 1-, 3- or 5-layers of thermally reduced graphene oxide (rGO) onto glass fabric surface according to the number of dips of the fabrics into GO solution. The electrical resistances from all electrode pairs were simultaneously and continuously recorded during distinct stages of the VARTM process to determine the relative conductance. During the vacuum cycle, the range of relative conductance increased with the number of coated rGO layers, with the 5-layer rGO-coated sensor showing the highest conductance range of 16.9 %. Additionally, it was observed that the 5-layer coated sensor showed a consistent decrease in conductance during the infusion phase due to the fluid flow pressure dominating the resin electrical conductivity.

Progress in food packaging applications of biopolymer-nanometal composites - A comprehensive review.

Eco-friendly nanotechnology-enabled biopolymers are one of the novel concepts of packaging materials to substitute traditional synthetic polymers and their composites. This article succinctly reviews the recent developments of introducing additional functionalities to biopolymers using metal and metal oxide nanoparticles. The functionality of metal nanoparticles such as silver, zinc oxide, titanium dioxide, copper oxide, gold, and magnesium oxide, as food packaging materials were discussed. The addition of nanoparticles in biopolymers improves mechanical properties, gas barrier properties, durability, temperature stability, moisture stability, antimicrobial activity, antioxidant property, and UV absorbance and can prevent the presence of ethylene and oxygen, hence extending the shelf life of foodstuffs. Other than this, the functional activity of these biopolymer composite films helps them to act like smart or intelligent packaging. The selection of metal nanoparticles, particle migration, toxicological effect, and potential future scope in the food packaging industry are also reviewed.

Magnetically Cured Macroradical Epoxy as Antimicrobial Coating.

The radical-bearing epoxy monomer could be the ideal embodiment of multifunctionality in epoxy-based materials. This study demonstrates the potential of macroradical epoxies as surface coating materials. A diepoxide monomer derivatized with a stable nitroxide radical is polymerized with a diamine hardener under the influence of a magnetic field. The magnetically oriented and stable radicals in the polymer backbone render the coatings antimicrobial. The unconventional use of magnets during polymerization proved crucial in correlating the structure-property relationships with antimicrobial performance inferred from oscillatory rheological technique, polarized macro-attenuated total reflectance - infrared (macro-ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The magnetic thermal curing influenced the surface morphology, resulting in a synergy of the coating's radical nature with microbiostatic performance assessed using the Kirby-Bauer test and liquid chromatography - mass spectroscopy (LC-MS). Further, the magnetic curing of blends with a traditional epoxy monomer demonstrates that radical alignment is more critical than radical density in imparting biocidal behavior. This study shows how the systematic use of magnets during polymerization could pave for probing more significant insights into the mechanism of antimicrobial action in radical-bearing polymers.

Highly Toughened Nanostructured Self-Assembled Epoxy-Based Material-Correlation Study between Nanostructured Morphology and Fracture Toughness-Impact Characteristics.

We present an efficient and effective method for preparing a novel self-assembled nanostructured material with high toughness and impact strength from a blend of di-glycidyl ether of bisphenol-A (DGEBA) and epoxidized poly(styrene-block-butadiene-block-styrene) (eSBS55) tri-block copolymer. The field emission scanning electron microscopy and transmission electron microscope results show the nanostructured morphological characteristics of the blends. This study achieved the highest fracture toughness, with a fracture toughness in the form of critical stress intensity factors (KIC) value of 2.54 MPa m1/2, in epoxy/block copolymer blends compared to previous works in the field. The impact strength also increased by 116% compared to neat epoxy. This is a major advancement in epoxy toughening due to the use of a single secondary phase. The resulting highly tough and impact-resistant material is a promising candidate for coating applications in industries such as flooring, building, aerospace, and automobiles.

Crosslinking Rapidly Cured Epoxy Resin Thermosets: Experimental and Computational Modeling and Simulation Study.

The power of computational modeling and simulation for establishing clear links between materials' intrinsic properties and their atomic structure has more and more increased the demand for reliable and reproducible protocols. Despite this increased demand, no one approach can provide reliable and reproducible outcomes to predict the properties of novel materials, particularly rapidly cured epoxy-resins with additives. This study introduces the first computational modeling and simulation protocol for crosslinking rapidly cured epoxy resin thermosets based on solvate ionic liquid (SIL). The protocol combines several modeling approaches, including quantum mechanics (QMs) and molecular dynamics (MDs). Furthermore, it insightfully provides a wide range of thermo-mechanical, chemical, and mechano-chemical properties, which agree with experimental data.

Upcycling Polystyrene.

Several environmental and techno-economic assessments highlighted the advantage of placing polystyrene-based materials in a circular loop, from production to waste generation to product refabrication, either following the mechanical or thermochemical routes. This review provides an assortment of promising approaches to solving the dilemma of polystyrene waste. With a focus on upcycling technologies available in the last five years, the review first gives an overview of polystyrene, its chemistry, types, forms, and varied applications. This work presents all the stages that involve polystyrene's cycle of life and the properties that make this product, in mixtures with other polymers, command a demand on the market. The features and mechanical performance of the studied materials with their associated images give an idea of the influence of recycling on the structure. Notably, technological assessments of elucidated approaches are also provided. No single approach can be mentioned as effective per se; hybrid technologies appear to possess the highest potential. Finally, this review correlates the amenability of these polystyrene upcycling methodologies to frontier technologies relating to 3D printing, human space habitation, flow chemistry, vertical farming, and green hydrogen, which may be less intuitive to many.

Nanocellulose: A Fundamental Material for Science and Technology Applications.

Recently, considerable interest has been focused on developing greener and biodegradable materials due to growing environmental concerns. Owing to their low cost, biodegradability, and good mechanical properties, plant fibers have substituted synthetic fibers in the preparation of composites. However, the poor interfacial adhesion due to the hydrophilic nature and high-water absorption limits the use of plant fibers as a reinforcing agent in polymer matrices. The hydrophilic nature of the plant fibers can be overcome by chemical treatments. Cellulose the most abundant natural polymer obtained from sources such as plants, wood, and bacteria has gained wider attention these days. Different methods, such as mechanical, chemical, and chemical treatments in combination with mechanical treatments, have been adopted by researchers for the extraction of cellulose from plants, bacteria, algae, etc. Cellulose nanocrystals (CNC), cellulose nanofibrils (CNF), and microcrystalline cellulose (MCC) have been extracted and used for different applications such as food packaging, water purification, drug delivery, and in composites. In this review, updated information on the methods of isolation of nanocellulose, classification, characterization, and application of nanocellulose has been highlighted. The characteristics and the current status of cellulose-based fiber-reinforced polymer composites in the industry have also been discussed in detail.

Magnetic field induced alignment of macroradical epoxy for enhanced electrical properties.

Improving the electrical performance of macroradical epoxy thermosets to surpass the semiconductor threshold requires a comprehensive understanding of the electrical charge transport mechanisms and characteristics. In this study, we investigate the electrical properties of a non-conjugated radical thermoset in a rigid, three-dimensional (3D) motif cured under an external magnetic field. The outcomes of the four-angle analysis of the synchrotron IRM beamline provide for the first time quantitative insights into the molecular orientation at the atomic-scale level. These insights, in turn, were utilized to apply Quantum Computational modeling theories and Monte Carlo simulation to study the effect of the magnetic field-induced molecular alignment on tuning electrical charge transport characteristics. The results explored the impact of radical density on forming percolation networks, showing a robust protocol for designing polymers with high electrical/thermal conductivity.

Core-Shell Nanofibers of Polyvinylidene Fluoride-based Nanocomposites as Piezoelectric Nanogenerators.

Flexible piezoelectric nanogenerators (PENG) are widely applied to harvest sustainable energy from multiple energy sources. The rational and simple design of PENG have great potential in soft electronics. Here we design a highly flexible PENG using the polyvinylidene fluoride (PVDF) and its copolymer, polyvinylidene hexafluoropropylene (PVDF-HFP) with two nanoarchitectures of semiconducting metal oxides, TiO2 and ZnO. The nanotubes of TiO2 and nanoflowers of ZnO are embedded in these different polymeric media by solvent mixing, and new fiber mats are generated by coaxial electrospinning technique. This process aligns the dipoles of polymers and nanomaterials, which is normally a pre-requisite for higher piezo potential. With excellent mechanical strength and flexibility, the tailored lightweight fiber mats are capable of producing good output voltage (a maximum of 14 V) during different mechanical vibrations at various frequencies and in response to human motions. The hybrid nanocomposite PENG is durable and inexpensive and has possible applications in wearable electronics.

Evolving Strategies for Producing Multiscale Graphene-Enhanced Fiber-Reinforced Polymer Composites for Smart Structural Applications.

Graphene has become an important research focus in many current fields of science including composite manufacturing. Developmental work in the field of graphene-enhanced composites has revealed several functional and structural characteristics that promise great benefits for their use in a broad range of applications. There has been much interest in the production of multiscale high-performance, lightweight, yet robust, multifunctional graphene-enhanced fiber-reinforced polymer (gFRP) composites. Although there are many reports that document performance enhancement in materials through the inclusion of graphene nanomaterials into a matrix, or its integration onto the reinforcing fiber component, only a few graphene-based products have actually made the transition to the marketplace. The primary focus of this work concerns the structural gFRPs and discussion on the corresponding manufacturing methodologies for the effective incorporation of graphene into these systems. Another important aspect of this work is to present recent results and highlight the excellent functional and structural properties of the resulting gFRP materials with a view to their future applications. Development of clear standards for the assessment of graphene material properties, improvement of existing materials and scalable manufacturing technologies, and specific regulations concerning human health and environmental safety are key factors to accelerate the successful commercialization of gFRPs.

Graphene based room temperature flexible nanocomposites from permanently cross-linked networks.

Graphene based room temperature flexible nanocomposites were prepared using epoxy thermosets for the first time. Flexible behavior was induced into the epoxy thermosets by introducing charge transfer complexes between functional groups within cross linked epoxy and room temperature ionic liquid ions. The graphene nanoplatelets were found to be highly dispersed in the epoxy matrix due to ionic liquid cation-π interactions. It was observed that incorporation of small amounts of graphene into the epoxy matrix significantly enhanced the mechanical properties of the epoxy. In particular, a 0.6 wt% addition increased the tensile strength and Young's modulus by 125% and 21% respectively. The electrical resistance of nanocomposites was found to be increased with graphene loading indicating the level of self-organization between the ILs and the graphene sheets in the matrix of the composite. The graphene nanocomposites were flexible and behave like ductile thermoplastics at room temperature. This study demonstrates the use of ionic liquid as a compatible agent to induce flexibility in inherently brittle thermoset materials and improve the dispersion of graphene to create high performance nanocomposite materials.

Evaluation of polyvinyl alcohol composite membranes containing collagen and bone particles.

Composite biomaterials provide alternative materials that improve on the properties of the individual components and can be used to replace or restore damaged or diseased tissues. Typically, a composite biomaterial consists of a matrix, often a polymer, with one or more fillers that can be made up of particles, sheets or fibres. The polymer matrix can be chosen from a wide range of compositions and can be fabricated easily and rapidly into complex shapes and structures. In the present study we have examined three size fractions of collagen-containing particles embedded at up to 60% w/w in a poly(vinyl alcohol) (PVA) matrix. The particles used were bone particles, which are a mineral-collagen composite and demineralised bone, which gives naturally cross-linked collagen particles. SEM showed well dispersed particles in the PVA matrix for all concentrations and sizes of particles, with FTIR suggesting collagen to PVA hydrogen bonding. Tg of membranes shifted to a slightly lower temperature with increasing collagen content, along with a minor amount of melting point depression. The modulus and tensile strength of membranes were improved with the addition of both particles up to 10 wt%, and were clearly strengthened by the addition, although this effect decreased with higher collagen loadings. Elongation at break decreased with collagen content. Cell adhesion to the membranes was observed associated with the collagen particles, indicating a lack of cytotoxicity.

Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design.

The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation.

Mechanical property and structure of covalent functionalised graphene/epoxy nanocomposites.

Thermally reduced graphene nanoplatelets were covalently functionalised via Bingel reaction to improve their dispersion and interfacial bonding with an epoxy resin. Functionalised graphene were characterized by microscopic, thermal and spectroscopic techniques. Thermal analysis of functionalised graphene revealed a significantly higher thermal stability compared to graphene oxide. Inclusion of only 0.1 wt% of functionalised graphene in an epoxy resin showed 22% increase in flexural strength and 18% improvement in storage modulus. The improved mechanical properties of nanocomposites is due to the uniform dispersion of functionalised graphene and strong interfacial bonding between modified graphene and epoxy resin as confirmed by microscopy observations.

Temperature variations at nano-scale level in phase transformed nanocrystalline NiTi shape memory alloys adjacent to graphene layers.

The detection and control of the temperature variation at the nano-scale level of thermo-mechanical materials during a compression process have been challenging issues. In this paper, an empirical method is proposed to predict the temperature at the nano-scale level during the solid-state phase transition phenomenon in NiTi shape memory alloys. Isothermal data was used as a reference to determine the temperature change at different loading rates. The temperature of the phase transformed zone underneath the tip increased by ∼3 to 40 °C as the loading rate increased. The temperature approached a constant with further increase in indentation depth. A few layers of graphene were used to enhance the cooling process at different loading rates. Due to the presence of graphene layers the temperature beneath the tip decreased by a further ∼3 to 10 °C depending on the loading rate. Compared with highly polished NiTi, deeper indentation depths were also observed during the solid-state phase transition, especially at the rate dependent zones. Larger superelastic deformations confirmed that the latent heat transfer through the deposited graphene layers allowed a larger phase transition volume and, therefore, more stress relaxation and penetration depth.

Individual dispersion of carbon nanotubes in epoxy via a novel dispersion-curing approach using ionic liquids.

The effective dispersion of carbon nanotubes (CNTs) in a thermoset was achieved using ionic liquid as the dispersion-curing agent. We preferentially dispersed multiwalled carbon nanotubes (MWCNTs) down to individual tube levels in epoxy resin. Here the dispersion is ruled by the depletion of physical bundles within the MWCNT networks, for which molecular ordering of ionic liquids is considered responsible. The quantitative analyses using ultra small angle X-ray scattering (USAXS) confirmed the dispersion of individual MWCNTs in the matrix. The distance between the dispersed nanotubes was calculated at different nanotube loadings using the power law fitting of the USAXS data. The fine dispersion and subsequent curing, both controlled by ionic liquid, lead to composites with substantially enhanced fracture mechanical and thermomechanical properties with no reduction in thermal properties. Merging processing techniques of nanocomposites with ionic liquid for efficient dispersion of nanotubes and preferential curing of thermosets facilitates the development of new, high performance materials.

Nanofibrillar micelles and entrapped vesicles from biodegradable block copolymer/polyelectrolyte complexes in aqueous media.

Here we report a viable route to fibrillar micelles and entrapped vesicles in aqueous solutions. Nanofibrillar micelles and entrapped vesicles were prepared from complexes of a biodegradable block copolymer poly(ethylene oxide)-block-poly(lactide) (PEO-b-PLA) and a polyelectrolyte poly(acrylic acid) (PAA) in aqueous media and directly visualized using cryogenic transmission electron microscopy (cryo-TEM). The self-assembly and the morphological changes in the complexes were induced by the addition of PAA/water solution into the PEO-b-PLA in tetrahydrofuran followed by dialysis against water. A variety of morphologies including spherical wormlike and fibrillar micelles, and both unilamellar and entrapped vesicles, were observed, depending on the composition, complementary binding sites of PAA and PEO, and the change in the interfacial energy. Increasing the water content in each [AA]/[EO] ratio led to a morphological transition from spheres to vesicles, displaying both the composition- and dilution-dependent micellar-to-vesicular morphological transitions.

Cellulose/polycaprolactone blends regenerated from ionic liquid 1-butyl-3-methylimidazolium chloride.

Ionic liquid solvent, 1-butyl-3-methylimidazolium chloride (BMIM[Cl]) was used to prepare cellulose/polycaprolactone (PCL) blend films. This solvent was recycled with high yield and purity after blend precipitation. The inter- and intra-molecular hydrogen bonding interactions in these blends were investigated by Fourier transform infrared (FTIR) spectroscopy and it was found that a new peak in the carbonyl region, assigned to hydrogen bonding between carbonyl groups of PCL and hydroxyl groups of cellulose in blends with PCL composition less than 40 wt%. Differential scanning calorimetry (DSC) results implied a partial miscibility of the two components by melting point depression. Moreover, the tensile properties of the blends can be adjusted by incorporating various amounts of PCL into cellulose. The blends show significant enhancement of thermal stability compared to the regenerated cellulose when the content of PCL is higher than 40 wt%. This work demonstrates an effective approach for the processing biodegradable blends from natural and synthetic polymers.

Microphase separation through competitive hydrogen bonding in self-assembled A-b-B/C diblock copolymer/homopolymer complexes.

We present a study of microphase separation induced by competitive hydrogen bonding in A-b-B/C diblock copolymer/homopolymer complexes where the diblock copolymer A-b-B is immiscible and the homopolymer C can interact unequally with both A and B blocks through hydrogen bonding. A model system containing poly(2-vinyl pyridine)-block-poly(methyl methacrylate) (P2VP-b-PMMA) and poly(4-vinyl phenol) (PVPh) in tetrahydrofuran was investigated. In these self-assembled complexes, microphase separation takes place due to the disparity in intermolecular interactions. Specifically, PVPh and P2VP blocks interact strongly to form complex, whereas PVPh and PMMA blocks interact weakly. The hydrogen bonding interactions were revealed by infrared spectroscopy and analyzed in terms of the difference in interassociation constants (K), i.e., interaction parameters of each blocks of the block copolymer to the homopolymer and according to the random phase approximation. The phase behavior of the complexes was investigated with small-angle x-ray scattering and transmission electron microscopy. A series of morphologies including lamellae, hexagonal cylinders, wormlike microdomains, and hierarchical structures was documented as a function of the copolymer concentration. Moreover, we outlined how hydrogen bonding determines the self-assembly and causes morphological transitions in different A-b-B/C diblock copolymer/homopolymer systems with respect to the K values.