Varying the degree of oxidation of graphite: effect of oxidation time and oxidant mass.

In this work, we employ a fast and less toxic modified Hummers' method to develop graphene oxide (GO) with varying degrees of oxidation and investigate the effect of the latter on the structure and the thermal properties of the synthesized materials. Two different key parameters, the time of the oxidation reaction and the mass of the oxidation agent, were systematically altered in order to fine tune the oxidation degree. All graphene oxides were characterized by a plethora of experimental techniques, like X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) as well as infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) for their structural, thermal and chemical identification. The results revealed that for a certain amount of oxidant, the time does not affect the final degree of oxidation of the materials, at least for the examined reaction times, because very similar structural patterns and thermal properties were obtained. At the same time, the oxygen-containing functional groups were found very similar. On the other hand, the degree of oxidation was found highly dependent on the mass of the oxidizing agent. XRD analysis showed a systematic increase of the interlayer distance of the synthesized GOs with the increase of the oxidant mass, whereas both the enthalpy of reduction and the % weight loss were increased. Moreover, XPS measurements provided a quantitative evaluation of the amount of carbon and oxygen in the materials; the increase of the oxidant mass led to a decrease of the total carbon content with the concurrent increase of the total oxygen amount.

The Role of Oxidation Pattern and Water Content in the Spatial Arrangement and Dynamics of Oxidized Graphene-Based Aqueous Dispersions.

In this work, we employ fully atomistic molecular dynamics simulations to elucidate the effects of the oxidation pattern and of the water content on the organization of graphene sheets in aqueous dispersions and on the dynamic properties of the different moieties at neutral pH conditions. Analysis of the results reveals the role of the oxidation motif (peripherally or fully oxidized flakes) in the tendency of the flakes to self-assemble and in the control of key structural characteristics, such as the interlayer distance between the sheets and the average size and the distribution of the formed aggregates. In certain cases, the results are compared to a pertinent experimental system, validating further the relevant computational models. Examination of the diffusional motion of the oxidized flakes shows that different degrees of spatial restriction are imposed upon the decrease in the water content and elucidates the conditions under which a motional arrest of the flakes takes place. At constant water content, the structural differences between the formed aggregates appear to additionally impart distinct diffusional characteristics of a water molecule. A detailed examination of the counterion dynamics describes their interaction with the oxidized flakes and their dependence on the water content and on the oxidation pattern, offering new insight into the expected electrical properties of the dispersions. The detailed information provided by this work will be particularly useful in applications such as molecular sieving, nanofiltration, and in cases where conductive membranes based on oxidized forms of graphene are used.

Tribological Performance Investigation of a Commercial Engine Oil Incorporating Reduced Graphene Oxide as Additive.

We investigated the tribological behavior of commercialized, fully synthetic engine oil upon the incorporation of reduced graphene oxide in seven different concentrations between 0.01 and 0.2 wt %. Stability of the prepared samples was assessed by turbidimetry and dynamic light scattering measurements, and their tribological properties through a reciprocating tribometer, using a steel ball on special cut steel blocks. The addition of 0.02 wt % of reduced graphene oxide led to an improvement of the tribological behavior compared to the pristine engine oil, by significantly lowering the friction coefficient by 5% in the boundary lubrication regime. Both the surfaces and the reduced graphene oxide additive were thoroughly characterized by microscopic and optical spectroscopy techniques. We also verified that a protective layer was formed between the worn surfaces, due to the presence of reduced graphene oxide. Carbon accumulation and various additive elements such as Ca, Zn, S and P were detected on the rubbing surfaces of both the ball and the block through energy-dispersive X-ray spectroscopy. Finally, it was shown that the wear scar diameter on the surface of the steel ball was lower by 3%, upon testing the engine oil sample containing reduced graphene oxide at concentration 0.02 wt %, compared to the control sample.