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Despite their excellent mechanical performance, carbon fiber-reinforced polymer (CFRP) composites are limited by the interfacial properties due to the inherent nature of laminated structures. One way to modify the interface is by the inclusion of nanomaterials. Here, we use electrochemical exfoliation to produce graphene (EEG) flakes that have hydroxyl and epoxy functional groups. To further improve the interfacial bonding, silanization was carried out on graphene with 3-aminopropyl triethoxysilane, and then, EEA flakes were achieved. Both flakes were dispersed in ethanol and spray-coated onto carbon fibers, followed by vacuum-assisted resin infusion to make hybrid composites. Testing of their mechanical properties showed that EEG flakes tend to act as points of stress concentration, which accelerated the delamination, while the EEA flakes improved interfacial properties owing to the covalent bonding. As a result, with only 0.5 wt % EEA flakes spray-coated onto the carbon fibers, the tensile and flexural strength of graphene/carbon fiber composites improved by 17.6 and 5.4%, respectively. The combination of electrochemical exfoliation, silanization, spray coating, and vacuum-assisted resin infusion enables large-scale hybrid composite fabrication without size or shape limitations, without weakening the CFs or carbon fabric patterns, and is suitable for continuous production. This process has proven to be practical and attractive for engineering applications.
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Epoxy composites with excellent thermal properties are highly promising for thermal management applications in modern electronic devices. In this work, we report the enhancement of the thermal conductivity of two different nanocomposites, using epoxy resins LY564 (epoxy 1) and LY5052 (epoxy 2), by incorporating multiwalled boron nitride nanotubes (BNNT) and boron nitride nanosheets (BNNS) as fillers. The synergistic interaction between the 1D BNNT and 2D BNNS allows for improved thermal conductivity via several different mechanisms. The highest thermal conductivity was measured at a loading of 1/30 wt % of BNNT/BNNS, resulting in values of 2.6 and 3.4 Wm-1 K-1, respectively, for each epoxy matrix. This improvement is attributed to the formation of a three-dimensional heat flow path formed through intercalation of the nanotubes between the BNNS. The thermal conductivity of the epoxy 1 and 2 nanocomposites improved by 940 and 1500%, respectively, making them suitable as thermal interface materials in electronic applications requiring electrical resistivity.
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MoS2 is a promising semiconducting material that has been widely studied for applications in catalysis and energy storage. The covalent chemical functionalization of MoS2 can be used to tune the optoelectronic and chemical properties of MoS2 for different applications. However, 2H-MoS2 is typically chemically inert and difficult to functionalize directly and thus requires pretreatments such as a phase transition to 1T-MoS2 or argon plasma bombardment to introduce reactive defects. Apart from being inefficient and inconvenient, these methods can cause degradation of the desirable properties and introduce unwanted defects. Here, we demonstrate that 2H-MoS2 can be simultaneously electrochemically exfoliated and chemically functionalized in a facile and scalable procedure to fabricate functionalized thin (â¼4 nm) MoS2 layers. The aryl diazonium salts used for functionalization have not only been successfully covalently grafted onto the 2H-MoS2, as verified by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, but also aid the exfoliation process by increasing the interlayer spacing and preventing restacking. Electrochemical energy storage is one application area to which this material is particularly suited, and characterization of supercapacitor electrodes using this exfoliated and functionalized material revealed that the specific capacitance was increased by â¼25% when functionalized. The methodology demonstrated for the simultaneous production and functionalization of two-dimensional (2D) materials is significant, as it allows for control over the flake morphology with increased repeatability. This electrochemical functionalization technique could also be extended to other types of transition-metal dichalcogenides (TMDs), which are also typically chemically inert with different functional species to adjust to specific applications.
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The potential for the use of copper coatings on steel switching mechanisms is abundant owing to the high conductivities and corrosion resistance that they impart on the engineered assemblies. However, applications of these coatings on such moving parts are limited due to their poor tribological properties; tendencies to generate high friction and susceptibility to degradative wear. In this study, we have fabricated a fluorinated graphene oxide-copper metal matrix composite (FGO-CMMC) on an AISI 52100 bearing steel substrate by a simple electrodeposition process in water. The FGO-CMMC coatings exhibited excellent lubrication performance under pin-on-disk (PoD) tribological sliding at 1N load, which reduced CoF by 63 and 69%, compared to the GO-CMMC and pure copper coatings that were also prepared. Furthermore, FGO-CMMC achieved low friction and low wear at higher sliding loads. The lubrication enhancement of the FGO-CMMCs is attributed to the tribochemical reaction of FGO with the AISI 52100 steel counterface initiated by the sliding load. The formation of an asymmetric tribofilm structure on the sliding track is critical; the performance of the FGO/Cu tribofilm formed in the track is boosted by the continued fluorination of the counterface surface during PoD sliding, passivating the tribosystem from adhesion-driven breakdown. The FGO-CMMC and GO-CMMC coatings also provide increased corrosion protection reaching 94.2 and 91.6% compared to the bare steel substrate, allowing for the preservation of the long-term low-friction performance of the coating. Other influences include the improved interlaminar shear strength of the FGO-containing composite. The excellent lubrication performance of the copper matrix composite coatings facilitated by FGO incorporation makes it a promising solid lubricant candidate for use in mechanical engineering applications.
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There is growing interest in graphene-reinforced inorganic matrix composites, but progress in this field is far behind that of polymer matrices due to difficulties in the processing of carbon materials in aggressive sintering environments, including oxidation and solubility in the host matrix. Copper-tungsten matrices are of particular interest in the power switching field but are difficult to produce due to the mutual insolubility of metals and poor wetting. Herein, composites were produced by decorating graphene oxide flakes with 8 nm diameter CuWO4·2H2O nanoparticles and then sintering them to form the final shape. The oxide nanoparticles were found to self-assemble into platelets on the surfaces of graphene flakes. Upon sintering, the presence of graphene was found to change the grain morphology from elongated needles to a polyhedral shape. It was found that, despite the nanosize of the CuWO4·2H2O particles used, the sintering conditions did not reduce the matrix to a pure metal; the sintered composites were found to be of mixed phase with copper tungstate and copper oxide present. Raman spectroscopy indicated that the graphene oxide became hydrogenated during the sintering process as a result of the reducing hydrogen atmosphere used.
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Copper-tungsten (Cu-W) composites are widely used in high-power and -temperature electrical applications. The combination of these metals, however, leads to compromised physical and electrical properties. Herein, we produce Cu-W-graphene oxide (Cu-W-GO) composites to address this challenge. To ensure uniform density composites, the as-received metal powders were flattened into a flake morphology by ball milling and then mixed with up to 0.5 wt.% GO flakes. The green forms were processed using spark plasma sintering. The GO was found to be well-dispersed amongst the metallic phases in the final composite. The addition of GO reduced the relative density of the composites slightly (4.7% decrease in relative density at 0.5 wt% GO loading for the composites processed at 1000 °C). X-ray diffraction confirmed good phase purity and that no carbide phases were produced. GO was found to improve the mechanical properties of the Cu-W, with an optimal loading of 0.1 wt.% GO found for ultimate compression strength and strain to failure, and 0.3 wt.% optimal loading for the 0.2% offset yield strength. Significantly, the electrical conductivity increased by up to 25% with the addition of 0.1 wt.% GO but decreased with higher GO loadings.
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The addition of graphene has been reported as a potential route to enhance the thermoelectric performance of SrTiO3. However, the interplay between processing parameters and graphene addition complicates understanding this enhancement. Herein, we examine the effects of processing parameters and graphene addition on the thermoelectric performance of La-doped SrTiO3 (LSTO). Briefly, two types of graphene oxide (GO) at different oxidation degrees were used, while the LSTO pellets were densified under two conditions with different reducing strengths (with/without using oxygen-scavenging carbon powder bed muffling). Raman imaging of the LSTO green body and sintered pellets suggests that the added GO sacrificially reacts with the lattice oxygen, which creates more oxygen vacancies and improves electrical conductivity regardless of the processing conditions. The addition of mildly oxidized electrochemical GO (EGO) yields better performance than the conventional heavily oxidized chemical GO (CGO). Moreover, we found that muffling the green body with an oxygen-scavenging carbon powder bed during sintering is vital to achieving a single-crystal-like temperature dependence of electrical conductivity, implying that a highly reducing environment is critical for eliminating the grain boundary barriers. Combining 1.0 wt % EGO addition with a highly reducing environment leads to the highest electrical conductivity of 2395 S cm-1 and power factor of 2525µW m-1 K-2 at 300 K, with an improved average zT value across the operating temperature range of 300-867 K. STEM-EELS maps of the optimized sample show a pronounced depletion of Sr and evident deficiency of O and La at the grain boundary region. Theoretical modeling using a two-phase model implies that the addition of GO can effectively improve carrier mobility in the grain boundary phase. This work provides guidance for the development of high-performance thermoelectric ceramic oxides.
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Transitional metal carbides and nitrides (MXenes) have promise for incorporation into multifunctional composites due to their high electrical conductivity and excellent mechanical and tribological properties. It is unclear, however, to what extent MXenes are also able to improve the mechanical properties of the composites and, if so, what would be the optimal flake size and morphology. Herein, Ti3C2Tx MXene is demonstrated to be indeed a good candidate for mechanical reinforcement in polymer matrices. In the present work, the strain-induced Raman band shifts of mono-/few-/multilayer MXenes flakes have been used to study the mechanical properties of MXene and the interlayer/interfacial stress transfer on a polymer substrate. The mechanical performance of MXene was found to be less dependent upon flake thickness compared to that of graphene. This enables Ti3C2Tx MXene to offer an efficient mechanical reinforcement to a polymer matrix with a flake length of >10 µm and a thickness of 10s of nanometers. Therefore, the degree of exfoliation of MXenes is not as demanding as other two-dimensional (2D) materials for the purpose of mechanical enhancement in polymers. In addition, the active surface chemistry of MXene facilitates possible functionalization to enable a stronger interface with polymers for applications, such as strain engineering and mechanical enhancement, and in materials including membranes, coatings, and textiles.
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Modulation of the grain boundary properties in thermoelectric materials that have thermally activated electrical conductivity is crucial in order to achieve high performance at low temperatures. In this work, we show directly that the modulation of the potential barrier at the grain boundaries in perovskite SrTiO3 changes the low-temperature dependency of the bulk material's electrical conductivity. By sintering samples in a reducing environment of increasing strength, we produced La0.08Sr0.9TiO3 (LSTO) ceramics that gradually change their electrical conductivity behavior from thermally activated to single-crystal-like, with only minor variations in the Seebeck coefficient. Imaging of the surface potential by Kelvin probe force microscopy found lower potential barriers at the grain boundaries in the LSTO samples that had been processed in the more reducing environments. A theoretical model using the band offset at the grain boundary to represent the potential barrier agreed well with the measured grain boundary potential dependency of conductivity. The present work showed an order of magnitude enhancement in electrical conductivity (from 85 to 1287 S cm-1) and power factor (from 143 to 1745 µW m-1 K-2) at 330 K by this modulation of charge transport at grain boundaries. This significant reduction in the impact of grain boundaries on charge transport in SrTiO3 provides an opportunity to achieve the ultimate "phonon glass electron crystal" by appropriate experimental design and processing.
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The traditional freeze-casting route for processing graphene-based aerogels is generally restricted to aqueously dispersed flakes of graphene oxide (GO) and post-processing reduction treatments, which brings restrictions to the aerogels electrical properties. In this work, we report a versatile aqueous processing route that uses the ability of GO todisperse graphene nanoplatelets (GNP) to produce rGO-GNP lamellar aerogels via unidirectional freeze-casting. In order to optimise the properties of the aerogel, GO-GNP dispersions were partially reduced by L-ascorbic acid prior to freeze-casting to tune the carbon and oxygen (C/O) ratio. The aerogels were then heat treated after casting to fully reduce the GO. The chemical reduction time was found to control the microstructure of the resulting aeorgels and thus to tune their electrical and mechanical properties. An rGO-GNP lamellar aerogel with density of 20.8 ± 0.8 mg cm-3 reducing using a reduction of 60 min achieved an electrical conductivity of 42.3 S m-1. On the other hand, an optimal reduction time of 35 min led to an aerogel with compressive modulus of 0.51 ±0.06 MPa at a density of 23.2 ± 0.7 mg cm-3, revealing a compromise between the tuning of electrical and mechanical properties. We show the present processing route can also be easily applied to produce lamellar aerogels on other graphene-based materials such as electrochemically exfoliated graphene.
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Graphene has been studied extensively for use in flexible electronics as ultrasensitive and wide-area strain sensors. Many sensors demonstrated so far rely on graphene networks, such that the spatial resolution is compromised, and they are unable to measure strain variations on a fine scale such as those resulting from substrate/interface failure. In this study, mono-/few-layer graphene are demonstrated to be good candidates for strain sensing with high spatial resolution to evaluate features <100 nm. The fundamentals of strain sensing-interaction with the target-have been discussed to shed light on the sensitivity and durability for future sensor fabrication. The proof-of-concept strain sensors have been shown to be able to monitor different states, e.g., the initiation and evolution, of crazes. The analysis also leads to the evaluation of interfacial energy and realization of high local strain in graphene that is applicable for other 2D materials for ultrasensitive strain sensing and bandgap opening applications.
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The chemical vapor deposition (CVD) of graphene on liquid substrates produces high quality graphene films due to the defect-free and atomically flat surfaces of the liquids. Through the detailed study of graphene growth on liquid Sn using atmospheric pressure CVD (APCVD), the quality of graphene has been found to have a close relationship with hydrogen flow rate that reflects on hydrogen partial pressure inside the reactor (PH2) and hydrogen solubility of the growth substrates. The role of PH2 was found to be crucial, with a low defect density monolayer graphene being obtained in low PH2 (90.4 mbar), while partial graphene coverage occurred at high PH2 (137.3 mbar). To further understand the role of substrate's composition, binary alloy with compositions of 20, 30, 50, 60 and 80 wt.% tin in copper were made by arc-melting. Graphene quality was found to decrease with increasing the content of copper in the Cu-Sn alloys when grown using the conditions optimised for Sn substrates and this was related to the change in hydrogen solubility and the high catalytic activity of Cu compared to Sn. This shall provide a tool to help optimising CVD conditions for graphene growth based on the properties of the used catalytic substrate.
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Interactive clothing requires sensing and display functionalities to be embedded on textiles. Despite the significant progress of electronic textiles, the integration of optoelectronic materials on fabrics remains as an outstanding challenge. In this Letter, using the electro-optical tunability of graphene, we report adaptive optical textiles with electrically controlled reflectivity and emissivity covering the infrared and near-infrared wavelengths. We achieve electro-optical modulation by reversible intercalation of ions into graphene layers laminated on fabrics. We demonstrate a new class of infrared textile devices including display, yarn, and stretchable devices using natural and synthetic textiles. To show the promise of our approach, we fabricated an active device directly onto a t-shirt, which enables long-wavelength infrared communication via modulation of the thermal radiation from the human body. The results presented here provide complementary technologies which could leverage the ubiquitous use of functional textiles.
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Poor cycling stability and mechanistic controversies have hindered the wider application of rechargeable aqueous Zn-MnO2 batteries. Herein, direct evidence was provided of the importance of Mn2+ in this type of battery by using a bespoke cell. Without pre-addition of Mn2+ , the cell exhibited an abnormal discharge-charge profile, meaning it functioned as a primary battery. By adjusting the Mn2+ content in the electrolyte, the cell recovered its charging ability through electrodeposition of MnO2 . Additionally, a dynamic pH variation was observed during the discharge-charge process, with a precipitation of Zn4 (OH)6 (SO4 )â 5H2 O buffering the pH of the electrolyte. Contrary to the conventional Zn2+ intercalation mechanism, MnO2 was first converted into MnOOH, which reverted to MnO2 through disproportionation, resulting in the dissolution of Mn2+ . The charging process occurred by the electrodeposition of MnO2 , thus improving the reversibility through the availability of Mn2+ ions in the solution.
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Electrodeposition of conducting polymer-carbon composites from an electrolyte precursor solution is a facile one-step approach to fabricate device-ready electrodes for energy storage. A key challenge in this approach is the dispersion of the carbon nanomaterials with the aqueous precursor solution with previous approaches either heavily oxidizing the carbon nanomaterials or using high concentrations of anionic surfactants as dopants. However, the former reduces the electrical conductivity of carbon, while the latter reduces the ionic mobility of the conducting polymer due to the large anion size. Herein, for the first time we present a quaternary electrolyte formulation for the fabrication of pristine carbon and polypyrrole (PPy) composites that does not sacrifice either electron or ion mobility. The electrolyte uses lithium perchlorate (20 mM) as a supporting electrolyte and dopant, sodium dodecylbenzenesulfonate at a very low concentration (1.43 mM) as a surfactant, together with pristine carbon nanomaterials and pyrrole monomers. The order of magnitude difference between the concentration of the dopant and surfactant ion allows the as-deposited PPy to be doped predominantly by small-sized and mobile perchlorate anions. Composites of PPy with carbon black, carbon nanotubes, and electrochemical exfoliated graphene (EEG) have been successfully prepared using this new quaternary electrolyte. The as-fabricated PPy/EEG composite electrodes showed a specific capacitance of 348.8 F g-1 with a high rate capability (190.7 F g-1 at 71 A g-1). Supercapacitor devices based on the PPy/EEG composite electrodes exhibit a high rate behavior up to 500 mV s-1 and a long cycle life of 5000 cycles.
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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.
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Morphing materials, also known as smart materials are attracting increasing attention as sensors, actuators and in soft robotic applications. In this work bilayered morphing composites were created by exploiting the thiol-ene photoclick reaction via maskless digital light processing (DLP). This technique allows for gradients and patterns of near infrared (nIR)-triggered materials to be efficiently crosslinked to substrates, with suitable interfacial adhesion to realise complex morphing. Photo-thermally responsive composites are produced by DLP patterning of reduced graphene oxide-filled chitosan-methacrylamide (rGO-chitosan-MA) on thiolated polydimethylsiloxane substrates via thiol-ene photoclick reaction. Morphing composites with parallel striped patterns and box-like hinges were printed via DLP to realise self-rolling and self-folding behaviours. Bilayered structures, with gradient rGO-chitosan-MA thicknesses (2-8 µm), were produced by controlling the light intensity from the DLP device. These gradient bilayered structures enable photothermal-triggered gradient bending and morphing exemplified here by a "walking worm" and a kirigami-inspired "opening flower". Thermo-mechanical calculations were performed to estimate bending angles, and finite element analysis applied to simulate self-folding and bending. The difference between simulation and measurements is in the range 0.4-7.6%, giving confidence to the assumptions and simplifications applied in design.
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Thin Mo2C hexagonal defects precipitate in CVD graphene when Mo crucibles are engaged to hold the liquid copper substrate, while these defects disappear when W crucibles are present. These defects have been identified as the thin precipitates of Mo2C. The growth mechanism of the Mo2C defects is demonstrated through thermodynamic calculations. This can be beneficial in graphene defect engineering through the vapour phase transport of the volatile MoO3 phase.
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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 (â¼2 GPa). The determination of the biaxial modulus of GNPs contributed to the evaluation of their Poisson's ratio (â¼0.34), which is very important but highly impractical to be measured directly on a nanoscale-sized specimen.
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Conductive inks for the future printed electronics should have the following merits: high conductivity, flexibility, low cost, and compatibility with wide range of substrates. However, the state-of-the-art conductive inks based on metal nanoparticles are high in cost and poor in flexibility. Herein, we reported a highly conductive, low cost, and super flexible ink based on graphene nanoplatelets. The graphene ink has been screen-printed on plastic and paper substrates. Combined with postprinting treatments including thermal annealing and compression rolling, the printed graphene pattern shows a high conductivity of 8.81 × 104 S m-1 and good flexibility without significant conductivity loss after 1000 bending cycles. We further demonstrate that the printed highly conductive graphene patterns can act as current collectors for supercapacitors. The supercapacitor with the printed graphene pattern as the current collector and printed activated carbon as the active material shows a good rate capability of up to 200 mV s-1. This work potentially provides a promising route toward the large-scale fabrication of low cost yet flexible printed electronic devices.