Nanomechanics of Ultrathin Carbon Nanomembranes.

Ultrathin carbon nanomembranes (CNMs) are two-dimensional materials (2DM) of a few nm thickness with sub-nm intrinsic pores that mimic the biofiltration membranes found in nature. They enable highly selective, permeable, and energy-efficient water separation and can be produced at large scales on porous substrates with tuned properties. The present work reports the mechanical performance of such CNMs produced by p-nitrobiphenyl phosphonic acid (NBPS) or polyvinylbiphenyl (PVBP) and their composite membranes of microporous supporting substrates, which constitute indispensable information for ensuring their mechanical stability during operation. Measuring the nanomechanical properties of the ultrathin material was achieved by atomic force microscopy (AFM) on membranes both supported on flat substrates and suspended on patterned substrates ("composite membrane"). The AFM analysis showed that the CNMs presented Young's modulus in the range of 2.5-8 GPa. The composite membranes' responses were investigated by tensile testing in a micro-tensile stage as a function of substrate thickness and substrate pore density and diameter, which were found to affect the mechanical properties. Thermogravimetric analysis was used to investigate the thermal stability of composite membranes at high temperatures. The results revealed the structural integrity of CNMs, while critical parameters governing their mechanical response were identified and discussed.

Wrinkle-mediated CVD synthesis of wafer scale Graphene/h-BN heterostructures.

The combination of two-dimensional materials (2D) into heterostructures enables their integration in tunable ultrathin devices. For applications in electronics and optoelectronics, direct growth of wafer-scale and vertically stacked graphene/hexagonal boron nitride (h-BN) heterostructures is vital. The fundamental problem, however, is the catalytically inert nature of h-BN substrates, which typically provide a low rate of carbon precursor breakdown and consequently a poor rate of graphene synthesis. Furthermore, out-of-plane deformations such as wrinkles are commonly seen in 2D materials grown by chemical vapor deposition (CVD). Herein, a wrinkle-facilitated route is developed for the fast growth of graphene/h-BN vertical heterostructures on Cu foils. The key advantage of this synthetic pathway is the exploitation of the increased reactivity from inevitable line defects arising from the CVD process, which can act as active sites for graphene nucleation. The resulted heterostructures are found to exhibit superlubric properties with increased bending stiffness, as well as directional electronic properties, as revealed from atomic force microscopy measurements. This work offers a brand-new route for the fast growth of Gr/h-BN heterostructures with practical scalability, thus propelling applications in electronics and nanomechanical systems.

Effective EMI shielding behaviour of thin graphene/PMMA nanolaminates in the THz range.

The use of graphene in a form of discontinuous flakes in polymer composites limits the full exploitation of the unique properties of graphene, thus requiring high filler loadings for achieving- for example- satisfactory electrical and mechanical properties. Herein centimetre-scale CVD graphene/polymer nanolaminates have been produced by using an iterative 'lift-off/float-on' process and have been found to outperform, for the same graphene content, state-of-the-art flake-based graphene polymer composites in terms of mechanical reinforcement and electrical properties. Most importantly these thin laminate materials show a high electromagnetic interference (EMI) shielding effectiveness, reaching 60 dB for a small thickness of 33 µm, and an absolute EMI shielding effectiveness close to 3·105 dB cm2 g-1 which is amongst the highest values for synthetic, non-metallic materials produced to date.

Multifunctional Cement Mortars Enhanced with Graphene Nanoplatelets and Carbon Nanotubes.

Recent findings have brought forward the potential of carbon nano-species, especially nanotubes and graphene, to impart exceptional multifunctional potential to cement, offering simultaneous enhancement of mechanical, fracture mechanical and electrical properties. While available knowledge on the topic is still limited, there is a complete absence of direct comparisons of the potential of the nano-species to improve strength and toughness and provide multifunctionality to the mortars. The study offers a comprehensive overview of these potentials, for mortars modified with pure graphene nanoplatelets and carbon nanotubes at consistent, directly comparable, concentrations up to 1.2 wt.%. Testing included flexure under pure bending moments, axial compression, electrical resistivity measurements and fracture tests under three point bending configuration; the latter were also independently assessed by acoustic emission. Differences in documented properties and optimal concentrations associated with improved mechanical performance were directly compared and rationalized in terms of nanospecies morphology. Dramatic, statistically consistent improvements in fracture behavior, up to 10-fold of control values, were documented for specific nanofiller concentrations, indicating an excellent potential of the material system for contemporary smart construction applications. An exceptionally favorable comparison of acoustic emission and fracture energy data confirmed that the non-destructive technique can independently assess the fracture performance of mortars with exceptional precision.

Mechanical, Electrical, and Thermal Properties of Carbon Nanotube Buckypapers/Epoxy Nanocomposites Produced by Oxidized and Epoxidized Nanotubes.

High volume fraction carbon nanotube (CNT) composites (7.5-16% vol.) were fabricated by the impregnation of CNT buckypapers into epoxy resin. To enhance the interfacial reaction with the epoxy resin, the CNTs were modified by two different treatments, namely, an epoxidation treatment and a chemical oxidation. The chemical treatment was found to result in CNT length severance and to affect the porosity of the buckypapers, having an important impact on the physico-mechanical properties of the nanocomposites. Overall, the mechanical, electrical, and thermal properties of the impregnated buckypapers were found to be superior of the neat epoxy resin, offering an attractive combination of mechanical, electrical, and thermal properties for multifunctional composites.

Tunable macroscale structural superlubricity in two-layer graphene via strain engineering.

Achieving structural superlubricity in graphitic samples of macroscale size is particularly challenging due to difficulties in sliding large contact areas of commensurate stacking domains. Here, we show the presence of macroscale structural superlubricity between two randomly stacked graphene layers produced by both mechanical exfoliation and chemical vapour deposition. By measuring the shifts of Raman peaks under strain we estimate the values of frictional interlayer shear stress (ILSS) in the superlubricity regime (mm scale) under ambient conditions. The random incommensurate stacking, the presence of wrinkles and the mismatch in the lattice constant between two graphene layers induced by the tensile strain differential are considered responsible for the facile shearing at the macroscale. Furthermore, molecular dynamic simulations show that the stick-slip behaviour does not hold for incommensurate chiral shearing directions for which the ILSS decreases substantially, supporting the experimental observations. Our results pave the way for overcoming several limitations in achieving macroscale superlubricity using graphene.

Graphene: A new activator of sodium persulfate for the advanced oxidation of parabens in water.

Graphene was successfully employed as a catalyst for the activation of sodium persulfate, towards the effective degradation of propylparaben, an emerging micro-pollutant, representative of the parabens family. A novel process is proposed which utilizes a commercial graphene nano-powder as the catalyst and sodium persulfate as the oxidizing agent. It was found that over 95% of micro-pollutant degradation occurs within 15 min of reaction time. The effects of catalyst loading (75 mg/L to 1 g/L), sodium persulfate (SPS) concentration (10 mg/L to 1 g/L), initial solution pH (3-9) and initial paraben concentration (0.5 mg/L to 5 mg/L) were examined. Experiments were carried out in different aqueous conditions, including ultrapure water, bottled water and wastewater in order to investigate their effect on the degradation rate. The efficiency of the process was lower at complex water matrices signifying the role of organic matter as scavenger of the oxidant species. The role of radical scavengers was also investigated through the addition of methanol and tert-butanol in several concentrations, which was found to be important only in relatively high values. An experiment in which propylparaben was substituted by methylparaben was conducted and similar results were obtained. The consumption of SPS was found to be high in all pH conditions tested, surpassing 80% in near neutral environment. However, the results indicate that the sulfate radicals formed react with water in alkaline conditions, which are the optimal for the reaction, producing hydroxyl radicals which appear to be the dominant species leading to the rapid degradation of propylparaben. To the best of our knowledge, this is the first time pristine graphene has been implemented as an activator of sodium persulfate for the effective oxidation of micro-pollutants.

Structural Properties of Chemically Functionalized Carbon Nanotube Thin Films.

Buckypapers are thin sheets of randomly entangled carbon nanotubes, which are highly porous networks. They are strong candidates for a number of applications, such as reinforcing materials for composites. In this work, buckypapers were produced from multiwall carbon nanotubes, pre-treated by two different chemical processes, either an oxidation or an epoxidation reaction. Properties, such as porosity, the mechanical and electrical response are investigated. It was found that the chemical pretreatment of carbon nanotubes strongly affects the structural properties of the buckypapers and, consecutively, their mechanical and electrical performance.