The development of new applications of graphene oxide in the biomedical field requires the covalent bonding of bioactive molecules to a sheet skeleton. Obtaining a large carboxyl group population over the surface is one of the main targets, as carboxyl group concentration in conventional graphene oxide is low among a majority of non-useful sp3-C-based functionalities. In the present work, we propose a selective method that yields an impressive increase in carboxyl group population using single-layer, thermally reduced graphene oxide as a precursor in a conventional Hummers–Offemann reaction. When starting with a reduced graphene oxide with no interlayer registry, sulfuric acid cannot form a graphite intercalated compound. Then, potassium permanganate attacks in in-plane (vacancies or holes) structural defects, which are numerous over a thermally reduced graphene oxide, as well as in edges, yielding majorly carboxyl groups without sheet cutting and unzipping, as no carbon dot formation was observed. A single-layer precursor with no ordered stacking prevents the formation of an intercalated compound, and it is this mechanism of the potassium permanganate that results in carboxyl group formation and the hydrophilic character of the compound.
In this study, CNTs and graphite have been incorporated to provide electrical conductivity and self-heating capacity by Joule effect to an epoxy matrix. Additionally, both types of fillers, with different morphology, surface area and aspect ratio, were simultaneously incorporated (hybrid CNTs and graphite addition) into the same epoxy matrix to evaluate the effect of the self-heating capacity of carbon materials-based resins on de-icing and ice-prevention capacity. The self-heating capacity by Joule effect and the thermal conductivity of the differently filled epoxy resin were evaluated for heating applications at room temperature and at low temperatures for de-icing and ice-prevention applications. The results show that the higher aspect ratio of the CNTs determined the higher electrical conductivity of the epoxy resin compared to that of the epoxy resin filled with graphite, but the 2D morphology of graphite produced the higher thermal conductivity of the filled epoxy resin. The presence of graphite enhanced the thermal stability of the filled epoxy resin, helping avoid its deformation produced by the softening of the epoxy resin (the higher the thermal conductivity, the higher the heat dissipation), but did not contribute to the self-heating by Joule effect. On the other hand, the feasibility of electrically conductive epoxy resins for de-icing and ice-prevention applications by Joule effect was demonstrated.
Different studies in the literature indicate the effectiveness of CNTs as reinforcing materials in cement–matrix composites due to their high mechanical strength. Nevertheless, their incorporation into cement presents some difficulties due to their tendency to agglomerate, yielding a non-homogeneous dispersion in the paste mix that results in a poor cement–CNTs interaction. This makes the surface modification of the CNTs by introducing functional groups on the surface necessary. In this study, three different treatments for incorporating polar oxygen functional groups onto the surface of carbon nanotubes have been carried out, with the objective of evaluating the influence of the type and oxidation degree on the mechanical and electrical properties and in strain-sensing function of cement pastes containing CNTs. One treatment is in liquid phase (surface oxidation with HNO3/H2SO4), the second is in gas phase (O3 treatment at 25 and 160 °C), and a third is a combination of gas-phase O3 treatment plus NaOH liquid phase. The electrical conductivity of cement pastes increased with O3- and O3-NaOH-treated CNTs with respect to non-treated ones. Furthermore, the oxygen functionalization treatments clearly improve the strain sensing performance of the CNT-cement pastes, particularly in terms of the accuracy of the linear correlation between the resistance and the stress, as well as the increase in the gage factor from 28 to 65. Additionally, the incorporation of either non-functionalized or functionalized CNTs did not produce any significant modification of the mechanical properties of CNTs. Therefore, the functionalization of CNTs favours the de-agglomeration of CNTs in the cement matrix and consequently, the electrical conductivity, without affecting the mechanical behaviour.