Origin of High Friction at Graphene Step Edges on Graphite.

On graphite, friction is known to be more than an order of magnitude larger at step edge defects as compared to on the basal plane, especially when the counter surface slides from the lower terrace of the step to the upper terrace. Very different mechanisms have been proposed to explain this phenomenon, including atomic interactions between the counter surface and step edge (without physical deformation) and buckling or peeling deformation of the upper graphene terrace. Here, we use atomic force microscopy (AFM) and reactive molecular dynamic (MD) simulations to capture and differentiate the mechanisms proposed to cause high friction at step edges. AFM experiments reveal the difference between cases of no deformation and buckling deformation, and the latter case is attributed to the physical stress exerted by the sliding tip. Reactive MD simulations explore the process of peeling deformation due to tribochemical bond formation between the tip and the step edge. Combining the results of AFM experiments and MD simulations, it is found that each mechanism has identifiable and characteristic features in the lateral force and vertical height profiles recorded during the step-up process. The results demonstrate that buckling and peeling deformation of the graphene edge rarely occur under typical AFM experimental conditions and thus are unlikely to be the origin of high friction at step edges in most measurements. Instead, the high step-up friction is due to stick-slip behavior facilitated by the topographical change and atomic interactions between the tip and step edge without deformation of the graphene itself.

Identifying Physical and Chemical Contributions to Friction: A Comparative Study of Chemically Inert and Active Graphene Step Edges.

Friction has both physical and chemical origins. To differentiate these origins and understand their combined effects, we study friction at graphene step edges with the same height and different terminating chemical moieties using atomic force microscopy (AFM) and reactive molecular dynamics (MD) simulations. A step edge produced by physical exfoliation of graphite layers in ambient air is terminated with hydroxyl (OH) groups. Measurements with a silica countersurface at this exposed step edge in dry nitrogen provide a reference where both physical topography effects and chemical hydrogen-bonding (H-bonding) interactions are significant. H-bonding is then suppressed in AFM experiments performed in alcohol vapor environments, where the OH groups at the step edge are covered with physisorbed alcohol molecules. Finally, a step edge buried under another graphene layer provides a chemically inert topographic feature with the same height. These systems are modeled by reactive MD simulations of sliding on an OH-terminated step edge, a step edge with alkoxide group termination, or a buried step edge. Results from AFM experiments and MD simulations demonstrate hysteresis in friction measured during the step-up versus step-down processes in all cases except the buried step edge. The origin of this hysteresis is shown to be the anisotropic deflection of terminal groups at the exposed step edge, which varies depending on their chemical functionality. The findings explain why friction is high on atomically corrugated and chemically active surfaces, which provides the insight needed to achieve superlubricity more broadly.

Effect of Ambient Chemistry on Friction at the Basal Plane of Graphite.

Graphite is widely used as a solid lubricant due to its layered structure, which enables ultralow friction. However, the lubricity of graphite is affected by ambient conditions and previous studies have shown a sharp contrast between frictional behavior in vacuum or dry environments compared to humid air. Here, we studied the effect of organic gaseous species in the environment, specifically comparing the adsorption of phenol and pentanol vapor. Atomic force microscopy experiments and reactive molecular dynamics simulations showed that friction was larger with phenol than with pentanol. The simulation results were analyzed to test multiple hypotheses to explain the friction difference, and it was found that mechanically driven chemical bonding between the tip and phenol molecules plays a critical role. Bonding increases the number of phenol molecules in the contact, which increases the adhesion as well as the number of atoms in registry with the topmost graphene layer acting as a pinning site to resist sliding. The findings of this research provide insight into how the chemistry of the operating environment can affect the frictional behavior of graphite and layered materials more generally.

Effect of Atomic Corrugation on Adhesion and Friction: A Model Study with Graphene Step Edges.

This Letter reports that the atomic corrugation of the surface can affect nanoscale interfacial adhesion and friction differently. Both atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that the adhesion force needed to separate a silica tip from a graphene step edge increases as the side wall of the tip approaches the step edge when the tip is on the lower terrace and decreases as the tip ascends or descends the step edge. However, the friction force measured with the same AFM tip moving across the step edge does not positively correlate with the measured adhesion, which implies that the conventional contact mechanics approach of correlating interfacial adhesion and friction could be invalid for surfaces with atomic-scale features. The chemical and physical origins for the observed discrepancy between adhesion and friction at the atomic step edge are discussed.

Chemical and physical origins of friction on surfaces with atomic steps.

Friction occurs through a complex set of processes that act together to resist relative motion. However, despite this complexity, friction is typically described using a simple phenomenological expression that relates normal and lateral forces via a coefficient, the friction coefficient. This one parameter encompasses multiple, sometimes competing, effects. To better understand the origins of friction, here, we study a chemically and topographically well-defined interface between silica and graphite with a single-layer graphene step edge. We identify the separate contributions of physical and chemical processes to friction and show that a single friction coefficient can be separated into two terms corresponding to these effects. The findings provide insight into the chemical and topographic origins of friction and suggest means of tuning surfaces by leveraging competing frictional processes.

Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

Mechanical characterization of diesel soot nanoparticles: in situ compression in a transmission electron microscope and simulations.

Incomplete fuel burning inside an internal combustion engine results in the creation of soot in the form of nanoparticles. Some of these soot nanoparticles (SNP) become adsorbed into the lubricating oil film present on the cylinder walls, which adversely affects the tribological performance of the lubricant. In order to better understand the mechanisms underlying the wear caused by SNPs, it is important to understand the behavior of SNPs and to characterize potential changes in their mechanical properties (e.g. hardness) caused by (or during) mechanical stress. In this study, the behavior of individual SNPs originating from diesel engines was studied under compression. The experiments were performed in a transmission electron microscope using a nanoindentation device. The nanoparticles exhibited elasto-plastic behavior in response to consecutive compression cycles. From the experimental data, the Young's modulus and hardness of the SNPs were calculated. The Young's modulus and hardness of the nanoparticles increased with the number of compression cycles. Using an electron energy loss spectroscopy technique, it was shown that the sp2/sp3 ratio within the compressed nanoparticle decreases, which is suggested to be the cause of the increase in elasticity and hardness. In order to corroborate the experimental findings, molecular dynamics simulations of a model SNP were performed. The SNP model was constructed using carbon and hydrogen atoms with morphology and composition comparable to those observed in the experiment. The model SNP was subjected to repeated compressions between two virtual rigid walls. During the simulation, the nanoparticle exhibited elasto-plastic behavior like that in the experiments. The results of the simulations confirm that the increase in the elastic modulus and hardness is associated with a decrease in the sp2/sp3 ratio.