Shear-activation of mechanochemical reactions through molecular deformation.

Mechanical stress can directly activate chemical reactions by reducing the reaction energy barrier. A possible mechanism of such mechanochemical activation is structural deformation of the reactant species. However, the effect of deformation on the reaction energetics is unclear, especially, for shear stress-driven reactions. Here, we investigated shear stress-driven oligomerization reactions of cyclohexene on silica using a combination of reactive molecular dynamics simulations and ball-on-flat tribometer experiments. Both simulations and experiments captured an exponential increase in reaction yield with shear stress. Elemental analysis of ball-on-flat reaction products revealed the presence of oxygen in the polymers, a trend corroborated by the simulations, highlighting the critical role of surface oxygen atoms in oligomerization reactions. Structural analysis of the reacting molecules in simulations indicated the reactants were deformed just before a reaction occurred. Quantitative evidence of shear-induced deformation was established by comparing bond lengths in cyclohexene molecules in equilibrium and prior to reactions. Nudged elastic band calculations showed that the deformation had a small effect on the transition state energy but notably increased the reactant state energy, ultimately leading to a reduction in the energy barrier. Finally, a quantitative relationship was developed between molecular deformation and energy barrier reduction by mechanical stress.

Effects of surface chemistry on the mechanochemical decomposition of tricresyl phosphate.

The growth of protective tribofilms from lubricant antiwear additives on rubbing surfaces is initiated by mechanochemically promoted dissociation reactions. These processes are not well understood at the molecular scale for many important additives, such as tricresyl phosphate (TCP). One aspect that needs further clarification is the extent to which the surface properties affect the mechanochemical decomposition. Here, we use nonequilibrium molecular dynamics (NEMD) simulations with a reactive force field (ReaxFF) to study the decomposition of TCP molecules confined and pressurised between sliding ferrous surfaces at a range of temperatures. We compare the decomposition of TCP on native iron, iron carbide, and iron oxide surfaces. We show that the decomposition rate of TCP molecules on all the surfaces increases exponentially with temperature and shear stress, implying that this is a stress-augmented thermally activated (SATA) process. The presence of base oil molecules in the NEMD simulations decreases the shear stress, which in turn reduces the rate constant for TCP decomposition. The decomposition is much faster on iron surfaces than iron carbide, and particularly iron oxide. The activation energy, activation volume, and pre-exponential factor from the Bell model are similar on iron and iron carbide surfaces, but significantly differ for iron oxide surfaces. These findings provide new insights into the mechanochemical decomposition of TCP and have important implications for the design of novel lubricant additives for use in high-temperature and high-pressure environments.

Understanding and Preventing Lubrication Failure at the Carbon Atomic Steps.

Two-dimensional (2D) lamellar materials are normally capable of rendering super-low friction, wear protection, and adhesion reduction in nanoscale due to their ultralow shear strength between two basal plane surfaces. However, high friction at step edges prevents the 2D materials from achieving super-low friction in macroscale applications and eventually leads to failure of lubrication performance. Here, taking graphene as an example, the authors report that not all step edges are detrimental. The armchair (AC) step edges are found to have only a minor topographic effect on friction, while the zigzag (ZZ) edges cause friction two orders of magnitude larger than the basal plane. The AC step edge is less reactive and thus more durable. However, the ZZ structure prevails when step edges are produced mechanically, for example, through mechanical exfoliation or grinding of graphite. The authors found a way to make the high-friction ZZ edge superlubricious by reconstructing the (6,6) hexagon structure to the (5,7) azulene-like structure through thermal annealing in an inert gas environment. This will facilitate the realization of graphene-based superlubricity over a wide range of industrial applications in which avoiding the involvement of step edges is difficult.

Shear-activated chemisorption and association of cyclic organic molecules.

Mechanochemical activation has created new opportunities for applications such as solvent-free chemical synthesis, polymer processing, and lubrication. However, mechanistic understanding of these processes is still limited because the mechanochemical response of a system is a complex function of many variables, including the direction of applied stress and the chemical features of the reactants in non-equilibrium conditions. Here, we studied shear-activated reactions of simple cyclic organic molecules to isolate the effect of chemical structure on reaction yield and pathway. Reactive molecular dynamics simulations were used to model methylcyclopentane, cyclohexane, and cyclohexene subject to pressure and shear stress between silica surfaces. Cyclohexene was found to be more susceptible to mechanochemical activation of oxidative chemisorption and subsequent oligomerization reactions than either methylcyclopentane or cyclohexane. The oligomerization trend was consistent with shear-driven polymerization yield measured in ball-on-flat sliding experiments. Analysis of the simulations showed the distribution of carbon atom sites at which oxidative chemisorption occurred and identified the double bond in cyclohexene as being the origin of its shear susceptibility. Lastly, the most common reaction pathways for association were identified, providing insight into how the chemical structures of the precursor molecules determined their response to mechanochemical activation.