We report the temporal evolution of the wettability of highly ordered pyrolytic graphite (HOPG) exposed to environmental conditions. Macroscopic wettability is investigated by static and dynamic contact angles (SCA and DCA) obtaining values comparable to the ones presented in the literature. SCA increases from ∼68° to ∼90° during the first hour of exposure after cleaving, whereas DCA is characterized by longer-scale (24 h) time evolution. We interpret these results in light of Fourier transform infrared spectroscopy, which indicates that the evolution of the HOPG wettability is due to adsorption of molecules from the surrounding atmosphere. This hypothesis is further confirmed by nanoscopic observations obtained by atomic force microscope (AFM)-based force spectroscopy, which monitor the evolution of surface properties with a spatial resolution superior to macroscopic experiments. Moreover, we observe that the results of macro- and nanoscale measurements evolve in similar fashion with time and we propose a quantitative correlation between SCA and AFM measurements. Our results suggest that the cause of the transition in the wettability of HOPG is due to the adsorption of hydrocarbon contaminations and water molecules from the environment. This is corroborated by annealing the HOPG is vacuum conditions at 150°, allowing the desorption of molecules on the surface, and thus re-establishing the initial macro and nano surface properties. Our findings can be used in the interpretation of the wettability of more complicated systems derived from HOPG (i.e., graphene).
Here we explore the raw parameter space in air in bimodal atomic force microscopy (AFM) in order to enhance resolution, provide multiparameter maps, and produce suitable transformations that lead to physically intuitive maps general enough to be recognized by the broader community, i.e., stiffness, Hamaker constant, and adhesion force. We further consider model free transforms to enhance the raw parameter space in the form of alternative and more intelligible contrast maps. We employ highly oriented pyrolytic graphite, calcite, polypropylene, and dsDNA on mica to demonstrate a systematic form of parameter expansion. The proposed methodology to enhance and interpret a larger parameter space introduces a methodology to tractable multidimensional AFM from raw bimodal AFM maps.
Vertical stacking of monolayers via van der Waals assembly is an emerging field that opens promising routes toward engineering physical properties of two-dimensional (2D) materials. Industrial exploitation of these engineering heterostructures as robust functional materials still requires bounding their measured properties so to enhance theoretical tractability and assist in experimental designs. Specifically, the shortrange attractive van der Waals forces are responsible for the adhesion of chemically inert components and are recognized to play a dominant role in the functionality of these structures. Here we reliably quantify the the strength of van der Waals forces in terms of an effective Hamaker parameter for CVD-grown graphene and show how it scales by a factor of two or three from single to multiple layers on standard supporting surfaces such as copper or silicon oxide. Furthermore, direct measurements on freestanding graphene provide the means to discern the interplay between the van der Waals potential of graphene and its supporting substrate. Our results demonstrated that the underlying substrates could enhance or reduce the van der Waals force of graphene surfaces, and its consequences are explained in terms of a Lifshitz theorybased analytical model.
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