Superlubricity of tetrahedral amorphous carbon (ta-C) coatings under boundary lubrication with organic friction modifiers is important for industrial applications, but the underlying mechanisms ...remain elusive. Here, combined experiments and simulations unveil a universal tribochemical mechanism leading to superlubricity of ta-C/ta-C tribopairs. Pin-on-disc sliding experiments show that ultra- and superlow friction with negligible wear can be achieved by lubrication with unsaturated fatty acids or glycerol, but not with saturated fatty acids and hydrocarbons. Atomistic simulations reveal that, due to the simultaneous presence of two reactive centers (carboxylic group and C=C double bond), unsaturated fatty acids can concurrently chemisorb on both ta-C surfaces and bridge the tribogap. Sliding-induced mechanical strain triggers a cascade of molecular fragmentation reactions releasing passivating hydroxyl, keto, epoxy, hydrogen and olefinic groups. Similarly, glycerol's three hydroxyl groups react simultaneously with both ta-C surfaces, causing the molecule's complete mechano-chemical fragmentation and formation of aromatic passivation layers with superlow friction.
Large-scale quantum molecular dynamics of water-lubricated diamond (111) surfaces in sliding contact reveals multiple friction regimes. While water starvation causes amorphization of the tribological ...interface, small H_{2}O traces are sufficient to preserve crystallinity. This can result in high friction due to cold welding via ether groups or in ultralow friction due to aromatic surface passivation triggered by tribo-induced Pandey reconstruction. At higher water coverage, Grotthuss-type diffusion and H_{2}O dissociation yield dense H/OH surface passivation leading to another ultralow friction regime.
Abstract
Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Our ...experiments show that DLC’s tribological behaviour in ZDDP-additivated oils can be optimised by tailoring its stiffness, surface nano-topography and hydrogen content. An optimal combination of ultralow friction and negligible wear is achieved using hydrogen-free tetrahedral amorphous carbon (ta-C) with moderate hardness. Softer coatings exhibit similarly low wear and thin ZDDP-derived patchy tribofilms but higher friction. Conversely, harder ta-Cs undergo severe wear and sub-surface sulphur contamination. Contact-mechanics and quantum-chemical simulations reveal that shear combined with the high local contact pressure caused by the contact stiffness and average surface slope of hard ta-Cs favour ZDDP fragmentation and sulphur release. In absence of hydrogen, this is followed by local surface cold welding and sub-surface mechanical mixing of sulphur resulting in a decrease of yield stress and wear.
Friction in boundary lubrication is strongly influenced by the atomic structure of the sliding surfaces. In this work, friction between dry amorphous carbon (a-C) surfaces with chemisorbed fragments ...of lubricant molecules is investigated employing molecular dynamic simulations. The influence of length, grafting density and polarity of the fragments on the shear stress is studied for linear alkanes and alcohols. We find that the shear stress of chain-passivated a-C surfaces is independent of the a-C density. Among all considered chain-passivated systems, those with a high density of chains of equal length exhibit the lowest shear stress. However, shear stress in chain-passivated a-C is consistently higher than in a-C surfaces with atomic passivation. Finally, surface passivation species with OH head groups generally lead to higher friction than their non-polar analogs. Beyond these qualitative trends, the shear stress behavior for all atomic- and chain-passivated, non-polar systems can be explained semi-quantitatively by steric interactions between the two surfaces that cause resistance to the sliding motion. For polar passivation species electrostatic interactions play an additional role. A corresponding descriptor that properly captures the interlocking of the two surfaces along the sliding direction is developed based on the maximum overlap between atoms of the two contacting surfaces.
Solid lubricants such as polytetrafluoroethylene (PTFE) are used in rolling-element bearings (REBs) when conventional lubrication (i.e. by fluids or greases) cannot be applied owing to extreme ...operating conditions (e.g. high temperatures or vacuum). Often a double transfer film mechanism is used with a cage acting as a lubricant reservoir resupplying the REB with solid lubricant by cage wear. An increase in service life of such bearings requires a better understanding of the transfer processes in the sliding and rolling contacts. Here, we investigate the effect of PTFE resupply on friction and lubricant film formation in a steel/steel and steel/glass rolling contact by tribometry and classical molecular dynamics (MD). A ball-on-disk tribometer is enhanced by a pin-on-disk sliding contact that transfers PTFE to the disk. The experiment allows simultaneous in situ measurement of friction and film thickness by white light interferometry in the rolling point contact. Increasing the pin load results in an increased PTFE film thickness in the rolling contact accompanied by a significant decrease in friction. To elucidate the observed film transfer and friction mechanism, sliding MD simulations with a newly developed density-functional-based, non-reactive force field for PTFE-lubricated iron oxide surfaces are performed. A strong adhesion of PTFE chains to iron oxide drives transfer film formation, whilst shear-induced chain alignment within PTFE results in reduced friction. The simulations reveal an anti-correlation between PTFE film thickness and friction coefficient—in agreement with the experiments. These investigations are a first step towards methods to control PTFE transfer film formation in REBs.
Graphic Abstract
A combination of atomistic simulations and vacuum tribometry allows atomic-scale insights into the chemical structure of superlubricious hydrogenated diamond-like carbon (a-C:H) interfaces in vacuum. ...Quantum molecular dynamics shearing simulations provide a structure-property map of the friction regimes that characterize the dry sliding of a-C:H. Shear stresses and structural properties at the sliding interfaces are crucially determined by the hydrogen content CH in the shear zone of the a-C:H coating. Extremely small CH (below 3 at.%) cause cold welding, mechanical mixing and high friction. At intermediate CH (ranging approximately from 3 to 20 at.%), cold welding in combination with mechanical mixing remains the dominant sliding mode, but some a-C:H samples undergo aromatization, resulting in a superlubricious sliding interface. A further increase in CH (above 20 at.%) prevents cold welding completely and changes the superlubricity mechanism from aromatic to hydrogen passivation. The hydrogen-passivated surfaces are composed of short hydrocarbon chains hinting at a tribo-induced oligomerization reaction. In the absence of cold welding, friction strongly correlates with nanoscale roughness, measured by the overlap of colliding protrusions at the sliding interface. Finally, the atomistic friction map is related to reciprocating friction experiments in ultrahigh vacuum. Accompanying X-ray photoelectron and Auger electron spectroscopy (XPS, XAES) analyses elucidate structural changes during vacuum sliding of a hydrogen-rich a-C:H with 36 at.% hydrogen. Initially, the a-C:H is covered by a nanometer-thick hydrogen-depleted surface layer. After a short running-in phase that results in hydrogen accumulation, superlubricity is established. XPS and XAES indicate a non-aromatic 1–2-nm-thick surface layer with polyethylene-like composition in agreement with our simulations.
The increasing demand for sustainable tribology has accelerated the development of environmentally friendly lubrication solutions such as water or water-related lubricants. Earlier works have ...reported on water-lubricated sliding of silicon nitride (Si3N4) at high speeds, which can result in a superlow friction (μ < 0.01) owing to the formation of hydrodynamic water films on hydrophilic surface layers. Here, combined boundary-lubrication experiments at low sliding speeds and atomistic simulations reveal an alternative superlubricity mechanism for glycerol-lubricated Si3N4. X-ray photoelectron and time-of-flight secondary ion mass spectrometry performed inside and outside the wear track as well as high-resolution mass spectroscopy of the used lubricant strongly suggest that sub-nanometer-thick graphene nitride layers form at the very top of Si3N4. In the accompanying atomistic simulations, glycerol molecules undergo tribochemical decomposition and react with surface-bound nitrogen atoms to form carbon nitrides. Further shearing promotes the formation of 2D graphene nitrides that passivate the ceramic surfaces and induce a superlow friction under boundary lubrication. Thus, glycerol-lubricated Si3N4 has a high potential for use in green superlubricity enabled by in situ synthesis of disordered graphene nitride species.
We present a quantum-accurate multiscale study of how hydrogen-filled discoidal "platelet" defects grow inside a silicon crystal. Dynamical simulations of a 10-nm-diameter platelet reveal that H2 ...molecules form at its internal surfaces, diffuse, and dissociate at its perimeter, where they both induce and stabilize the breaking up of highly stressed silicon bonds. A buildup of H2 internal pressure is neither needed for nor allowed by this stress-corrosion growth mechanism, at odds with previous models. Slow platelet growth up to micrometric sizes is predicted as a consequence, making atomically smooth crystal cleavage possible in implantation experiments.
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