Superlubricity mechanism of diamond-like carbon with glycerol. Coupling of experimental and simulation studies

We report a unique tribological system that produces superlubricity under boundary lubrication conditions with extremely little wear. This system is a thin coating of hydrogen-free amorphous Diamond-Like-Carbon (denoted as ta-C) at 353 K in a ta-C/ta-C friction pair lubricated with pure glycerol. To understand the mechanism of friction vanishing we performed ToF-SIMS experiments using deuterated glycerol and 13C glycerol. This was complemented by first-principles-based computer simulations using the ReaxFF reactive force field to create an atomistic model of ta-C. These simulations show that DLC with the experimental density of 3.24 g/cc leads to an atomistic structure consisting of a 3D percolating network of tetrahedral (sp3) carbons accounting for 71.5% of the total, in excellent agreement with the 70% deduced from our Auger spectroscopy and XANES experiments. The simulations show that the remaining carbons (with sp2 and sp1 character) attach in short chains of length 1 to 7. In sliding simulations including glycerol molecules, the surface atoms react readily to form a very smooth carbon surface containing OH-terminated groups. This agrees with our SIMS experiments. The simulations find that the OH atoms are mostly bound to surface sp1 atoms leading to very flexible elastic response to sliding. Both simulations and experiments suggest that the origin of the superlubricity arises from the formation of this OH-terminated surface

A comparative study on the functionality of S- and P-based lubricant additives by combined first principles and experimental analysis

Sulfur and phosphorus are key elements for the functionality of lubricant additives used in extreme pressure applications, such as synchronizer systems in cars. To understand their mechanism of action we combine first principles calculations and gas phase lubrication experiments. The surface spectroscopy analysis performed in situ after the tribological test indicates that iron sulfide (phosphide) is formed by rubbing steel-on-steel in the presence of organo-sulfur (-phosphorus) molecules. We, thus, study the effects of elemental sulfur and phosphorus on the interfacial properties of iron by spin-polarized density functional theory calculations. The results show that both the elements are very effective in reducing the adhesion and shear strength of iron. Sulfur is predicted to be more effective than phosphorus, especially at high pressure. Gas phase lubrication experiments confirm these results, indicating that the friction coefficient of iron-sulphide is lower than that of iron-phosphide and both S and P dramatically reduce the friction of steel-on-steel. These results indicate that the release of elemental sulfur and phosphorus may be the key mechanism to controlling the tribological properties of the metal interface and elucidate that the underling microscopic phenomenon is metal passivation. © 2016 The Royal Society of Chemistry.Sulfur and phosphorus are key elements for the functionality of lubricant additives used in extreme pressure applications, such as synchronizer systems in cars. To understand their mechanism of action we combine first principles calculations and gas phase lubrication experiments. The surface spectroscopy analysis performed in situ after the tribological test indicates that iron sulfide (phosphide) is formed by rubbing steel-on-steel in the presence of organo-sulfur (-phosphorus) molecules. We, thus, study the effects of elemental sulfur and phosphorus on the interfacial properties of iron by spin-polarized density functional theory calculations. The results show that both the elements are very effective in reducing the adhesion and shear strength of iron. Sulfur is predicted to be more effective than phosphorus, especially at high pressure. Gas phase lubrication experiments confirm these results, indicating that the friction coefficient of iron-sulphide is lower than that of iron-phosphide and both S and P dramatically reduce the friction of steel-on-steel. These results indicate that the release of elemental sulfur and phosphorus may be the key mechanism to controlling the tribological properties of the metal interface and elucidate that the underling microscopic phenomenon is metal passivation

Tribochemistry of phosphorus additives: Experiments and first-principles calculations

Organophosphorus compounds are common additives included in liquid lubricants for many applications, in particular automotive applications. Typically, organic phosphites function as friction-modifiers whereas phosphates as anti-wear additives. While the antiwear action of phosphates is now well understood, the mechanism by which phosphites reduce friction is still not clear. Here we study the tribochemistry of both phosphites and phosphates using gas phase lubrication (GPL) and elucidate the microscopic mechanisms that lead to the better frictional properties of phosphites. In particular, by in situ spectroscopic analysis we show that the friction reduction is connected to the presence of iron phosphide, which is formed by tribochemical reactions involving phosphites. The functionality of elemental phosphorus in reducing the friction of iron-based interfaces is elucidated by first principle calculations. In particular, we show that the work of separation and shear strength of iron dramatically decrease by increasing the phosphorus concentration at the interface. These results suggest that the functionality of phosphites as friction modifiers may be related to the amount of elemental phosphorus that they can release at the tribological interface

Superlubricity and tribochemistry of polyhydric alcohols

The anomalous low friction of diamondlike carbon coated surfaces lubricated by pure glycerol was observed at 80 °C. Steel surfaces were coated with an ultrahard 1 µm thick hydrogen-free tetrahedral coordinated carbon (ta-C) layer produced by physical vapor deposition. In the presence of glycerol, the friction coefficient is below 0.01 at steady state, corresponding to the so-called superlubricity regime (when sliding is then approaching pure rolling). This new mechanism of superlow friction is attributed to easy glide on triboformed OH-terminated surfaces. In addition to the formation of OH-terminated surfaces but at a lower temperature, we show here some evidence, by coupling experimental and computer simulations, that superlow friction of polyhydric alcohols could also be associated with triboinduced degradation of glycerol, producing a nanometer-thick film containing organic acids and water. Second, we show outstanding superlubricity of steel surfaces directly lubricated by a solution of myo-inositol (also called vitamin Bh) in glycerol at ambient temperature (25 °C). For the first time, under boundary lubrication at high contact pressure, friction of steel is below 0.01 in the absence of any long chain polar molecules. The mechanism is still unknown but could be associated with friction-induced dissociation of glycerol and interaction of waterlike species with steel surface

Formation of interfacial molybdenum carbide for DLC lubricated by MoDTC: Origin of wear mechanism

A large amount of research has been devoted to the effect of molybdenum dithiocarbamate (MoDTC) additives on the lubricating performances of carbon-based coatings, showing that a high wear rate is produced when the MoDTC is blended with the base oil. However, the mechanisms leading to the coating removal are not fully understood yet. In this work, the friction and wear performances of an amorphous hydrogenated DLC coating doped with silicon and oxygen have been analysed when lubricated by MoDTC-containing oils. Tribological experiments have been conducted with DLC/steel and DLC/DLC contacts under boundary lubrication conditions using a ball-on-flat tribometer. To understand the wear mechanism, the chemical composition of the tribofilm formed on the steel ball counterpart was investigated by X-ray Photoelectron Spectroscopy (XPS). Transmission Electron Microscopy (TEM) coupled with Energy Dispersive X-Ray Spectroscopy (EDX). A new DLC wear model has been proposed and validated

Adiabatic and entropy perturbations propagation in a bouncing Universe

By studying some bouncing universe models dominated by a specific class of hydrodynamical fluids, we show that the primordial cosmological perturbations may propagate smoothly through a general relativistic bounce. We also find that the purely adiabatic modes, although almost always fruitfully investigated in all other contexts in cosmology, are meaningless in the bounce or null energy condition (NEC) violation cases since the entropy modes can never be neglected in these situations: the adiabatic modes exhibit a fake divergence that is compensated in the total Bardeen gravitational potential by inclusion of the entropy perturbations.Comment: 25 pages, no figure, LaTe

A Semi-deterministic Wear Model Considering the Effect of Zinc Dialkyl Dithiophosphate Tribofilm

Tribochemistry plays a very important role in the behaviour of systems in tribologically loaded contacts under boundary lubrication conditions. Previous works have mainly reported contact mechanics simulations for capturing the boundary lubrication regime, but the real mechanism in which tribofilms reduce wear is still unclear. In this paper, the wear prediction capabilities of a recently published mechanochemical simulation approach (Ghanbarzadeh et al. in Tribol Int, 2014) are tested. The wear model, which involves a time- and spatially dependent coefficient of wear, was tested for two additive concentrations and three temperatures at different times, and the predictions are validated against experimental results. The experiments were conducted using a mini-traction machine in a sliding/rolling condition, and the spacer layer interferometry method was used to measure the tribofilm thickness. Wear measurements have been taken using a white-light interferometry. Good agreement is seen between simulation and experiment in terms of tribofilm thickness and wear depth predictions