The evolution of a sliding interface between two objects is difficult to theorize, predict, and measure due to the complexity of the interface, which is often described phenomenologically. Here we utilize the nanometer-scale single-asperity of an atomic force microscope sliding against atomically flat graphene and graphene oxide to study the origins of friction, wear, and tribofilm growth phenomena at the atomic scale. We hypothesize that all of the observed contact phenomena at the macroscale can be described using fundamental thermochemistry.  To test this hypothesis, we employ a number of AFM techniques to explore contact mechanics over a wide range of scanning speeds, applied loads, tip temperatures, and applied biases.  At low applied tip loads, the friction of graphene oxide is non-monotonic with tip velocity, initially increasing for speeds from 100 – 10,000 nm/s, followed by a decrease and a subsequent increase above 50,000 nm/s. At sufficiently high applied loads, we observe wear of oxygen groups from graphene oxide at temperatures between 50-400 °C and loads between 10-700 nN, and find an exponential increase in wear rate with applied load. For the case of an electrically biased tip oxidizing pristine graphene, the oxidation rate somewhat paradoxically increases with applied load, despite previously observed enhancement in wear rate with load. All of the above observations can be understood in the context of mechanically driven thermochemical reactions. The friction behavior depends on two competing factors—aging of the sliding contact due to chemical bonding between tip and substrate, and hopping of unbonded tip atoms between graphene lattice sites. Atomic wear of graphene oxide is well described by the tilted potential energy surface theory of mechanically driven chemistry, which predicts a non-linear reduction in the energy barrier with applied load. We further show that the tilted potential energy surface model also well describes the enhancement of oxidation rate. The work presented here creates a foundation for describing the mechanics of sliding contacts as chemical processes, and further paves the way towards quantitatively understanding how mechanical force drives chemical reactions in general.

Chemistry of friction, wear, and tribofilm growth on 2D materials

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.