Screening effect of CVD graphene on the surface free energy of substrates.

The wettability of graphene has been a topic under constant discussion in the literature since 2012. In this work we measured the contact angle (CA) of six different types of substrates (glass, quartz, Si3N4, Si/SiO2, sapphire and Si) with varying dielectric constants and surface roughnesses in order to calculate the surface free energy of graphene films to evaluate how the wetting properties of graphene-coated substrates are changed according to the underlying substrate. We used a residual-free transfer process to remove the high-quality graphene (CVD-Gr) grown onto copper foil. Afterwards, we performed an inert thermal treatment (Ar, at 300 °C for 30 minutes) to remove airborne contaminants from the graphene surface and evaluate the roughness of substrates by atomic force microscopy, the advancing and receding contact angles of two liquids (water and ethylene glycol), hysteresis, and surface free energy (polar and dispersive components) calculations. The presence of high-quality monolayer graphene (free of any air contaminants, polymer residues, etc.) led to a common wettability behaviour for all coated surfaces, regardless of the nature of the underlying substrate. This result can be understood in terms of the screening of van der Waals and dipole interactions by the electrons in graphene.

Understanding the unorthodox stabilization of liquid phase exfoliated molybdenum disulfide (MoS2) in water medium.

Molybdenum disulfide is a highly esteemed 2D material with interesting applications in nanoelectronics, composites, biotechnology and beyond. Its production through liquid-phase exfoliation in H2O is low-cost and eco-friendly. Herein, we present a detailed experimental and theoretical investigation seeking to explain the peculiar stability of MoS2 in H2O medium. By combining different microscopic (SEM, AFM and OM), spectrometric (Raman, UV-vis and AFM-FTIR), scattering (DLS) and ab initio simulation techniques, an edge-functionalization hypothesis for the excellent solvent properties of water for producing few-layer MoS2 has been demonstrated.

Ultrafast charge transfer dynamics pathways in two-dimensional MoS2-graphene heterostructures: a core-hole clock approach.

Two-dimensional van der Waals heterostructures are attractive candidates for optoelectronic nanodevice applications. The charge transport process in these systems has been extensively investigated, however the effect of coupling between specific electronic states on the charge transfer process is not completely established yet. Here, interfacial charge transfer (CT) in the MoS2/graphene/SiO2 heterostructure is investigated from static and dynamic points of view. Static CT in the MoS2-graphene interface was elucidated by an intensity quenching, broadening and a blueshift of the photoluminescence peaks. Atomic and electronic state-specific CT dynamics on a femtosecond timescale are characterized using a core-hole clock approach and using the S1s core-hole lifetime as an internal clock. We demonstrate that the femtosecond electron transfer pathway in the MoS2/SiO2 heterostructure is mainly due to the electronic coupling between S3p-Mo4d states forming the Mo-S covalent bond in the MoS2 layer. For the MoS2/graphene/SiO2 heterostructure, we identify, with the support of density functional calculations, new pathways that arise due to the high density of empty electronic states of the graphene conduction band. The latter makes the transfer process time in the MoS2/graphene/SiO2/Si twice as fast as in the MoS2/SiO2/Si sample. Our results show that ultrafast electron delocalization pathways in van der Waals heterostructures are dependent on the electronic properties of each involved 2D material, creating opportunities to modulate their transport properties.

Thermal Transport and Rheological Properties of Hybrid Nanofluids Based on Vegetable Lubricants.

Nanofluids based on vegetal oil with different wt.% of carbon nanotubes (CNT), hexagonal boron nitride (h-BN), and its hybrid (h-BN@CNT) were produced to investigate the effects of these nano-additives on the thermal conductivity and rheological properties of nanofluids. Stable suspensions of these oil/nanostructures were produced without the use of stabilizing agents. The dispersed nanostructures were investigated by SEM, EDS, XRD, and XPS, while the thermal conductivity and rheological characteristics were studied by a transient hot-wire method and steady-state flow tests, respectively. Increases in thermal conductivity of up to 39% were observed for fluids produced with 0.5 wt.% of the hybrid nanomaterials. As for the rheological properties, it was verified that both the base fluid and the h-BN suspensions exhibited Newtonian behavior, while the presence of CNT modified this tendency. This change in behavior is attributed to the hydrophobic character of both CNT and the base oil, while h-BN nanostructures have lip-lip "bonds", giving it a partial ionic character. However, the combination of these nanostructures was fundamental for the synergistic effect on the increase of thermal conductivity with respect to their counterparts.

High-Tribological-Performance Polymer Nanocomposites: An Approach Based on the Superlubricity State of the Graphene Oxide Agglomerates.

Here, nanocomposites of high-molecular-weight polyethylene (HMWPE) and HMWPE-UHMWPE (80/20 wt.%) containing a low amount of multilayer graphene oxide (mGO) (≤0.1 wt.%) were produced via twin-screw extrusion to produce materials with a higher tribological performance than UHMWPE. Due to the high viscosity of both polymers, the nanocomposites presented a significant concentration of agglomerates. However, the mechanical (tensile) and tribological (volumetric loss) performances of the nanocomposites were superior to those of UHMWPE. The morphology of the nanocomposites was investigated using differential scanning calorimetry (DSC), microtomography, and transmission electron microscopy (TEM). The explanation for these results is based on the superlubricity phenomenon of mGO agglomerates. It was also shown that the well-exfoliated mGO also contained in the nanocomposite was of fundamental importance as a mechanical reinforcement for the polymer. Even with a high concentration of agglomerates, the nanocomposites displayed tribological properties superior to UHMWPE's (wear resistance up to 27% higher and friction coefficient up to 57% lower). Therefore, this manuscript brings a new exception to the rule, showing that agglomerates can act in a beneficial way to the mechanical properties of polymers, as long as the superlubricity phenomenon is present in the agglomerates contained in the polymer.