B. Vacher

Mechanisms of ultra-low friction by hollow inorganic fullerene-like MoS2 nanoparticles

Abstract Inorganic Fullerene-like (IF)-MoS2 nanoparticles were tested under boundary lubrication and ultra-high vacuum (UHV) and were found to give an ultra-low friction coefficient in both cases compared to hexagonal (h)-MoS2 material. Previous works made by Rapoport et al. with IF-WS2 revealed that the benefit effect of the inorganic fullerene-like materials decreases at high loads and sliding velocities. Nevertheless, under the conditions used in our experiments using high contact pressure (maximum pressure above 1.1 GPa in oil and 400 MPa in high vacuum) and slow sliding velocities (1.7 mm/s in oil test and 1 mm/s in high vacuum), friction always decreases and stabilizes at about 0.04 for 800 cycles in both cases. Therefore, IF-MoS2 material appears to be a good candidate for use in various environments in regard to other MoS2 crystal structures. Wear mechanisms were investigated using both High Resolution TEM and surface analyses (XPS) on the wear tracks. Wear particles collected from the flat wear scar show several morphologies, suggesting at least two lubricating mechanisms. As spherical particles are found in the wear debris, rolling may be a possible event. However, flattened and unwrapped IF-MoS2 particles are often observed after friction. In this case, low friction is thought to be due either to sliding between IF-MoS2 external flattened planes or to slip between individual unwrapped MoS2 sheets.

Synergistic effects in binary systems of lubricant additives: a chemical hardness approach

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and detergent overbased calcium borate (CB) lubricant additives have been investigated by coupling analytical TEM and micro‐spot XPS in the tribotester Optimol of SRV GmbH (mild wear conditions in boundary lubrication). Synergistic effects have been observed on both friction and wear data, especially in the Modtc/Zndtp combination. Results have been interpreted on the basis of a chemical hardness concept: the hard and soft acids and bases (HSAB) principle, stabilisation of hard–hard pairs and the maximum hardness principle. The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS2 single sheets and the digestion of MoO3, which is also formed, by the zinc polyphosphate glass. The final result of the tribochemical reaction is a tribofilm composed of MoS2 sheets embedded in a mixed Mo/Zn polyphosphate glass. The CB/Modtc mixture has a similar mechanism except that the oxide is not completely eliminated, due to the softer borate anion compared with the phosphate one.

Antiwear film formation of neutral and basic ZDDP: influence of the reaction temperature and of the concentration

Both synchrotron radiation-based techniques (XANES) and transmission electron microscopy (EDX, EELS) are used to draw a comparison of antiwear and thermal films generated from neutral and basic ZDDP salts. Antiwear films were created in a pin-on-flat wear machine and the wear debris was collected. The analysis of the tribofilms did not show any substantial difference between neutral and basic ZDDPs. The wear scar diameter and the P and S chemical environment in the tribofilm were very similar. The chemical analysis of the wear debris revealed differences in the chemical composition. Wear debris from basic ZDDP seems to be mostly composed either of unreacted ZDDP or of a linkage isomer of ZDDP (LI-ZDDP), and zinc polyphosphate; whereas the wear debris as far as neutral ZDDP is concerned seems to be exclusively composed of zinc polyphosphate (and sulphur species). More iron was also detected in the wear debris with basic ZDDP – possibly an indication of the iron content of the tribofilm. Differences in chemical structure could also be detected in the thermal films. While neutral ZDDP reacted with the surface to form polyphosphates at 150°C, the same reaction products were obtained with basic ZDDP at 175°C. The concentration of ZDDP in oil is thought to be the main parameter to explain the differences in the thermal film formation.

A dual‐analysis approach in tribochemistry: application to ZDDP/calcium borate additive interactions

Tribochemical interactions between zinc dithiophosphate (ZDDP) and micellar calcium borate (CB) under boundary lubrication were investigated by coupling, in the same location of the wear track, both analytical TEM analysis of collected wear fragments from the tribofilm and XPS surface analysis of the tribofilm directly underneath. This is the so‐called dual‐analysis approach, which improves the interpretation of tribochemical reactions. The elemental composition inside the wear scars was analysed by micro‐spot XPS. By depth profiling, the film thickness could also be determined. In particular, the efficiency of the additive combination could be proven by quantification of iron oxide. The nature of wear particles was investigated in the TEM by using EELS and EDX simultaneously, with the result that phosphorus, boron and sulphur contributions have been carefully distinguished. The technique is very powerful for determining the composition of the material through quantification of both EELS and EDX spectra on the same specimen. The main result, when ZDDP and CB additives are used together, is the formation of a calcium and zinc borophosphate glass tribofilm. The overall data confirm the general friction‐induced glass model as being a unifying concept that explains the mechanisms of antiwear additives under boundary lubrication. Moreover, the analytical results strongly suggest the role of viscous flow of the magma state glass tribofilm above its glass transition temperature to be a main contribution to the antiwear mechanism under mild wear conditions.

Tribochemical interactions between Zndtp, Modtc and calcium borate

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and overbased detergent calcium borate (OCB) lubricant additives have been investigated. Friction tests were performed in mild wear conditions under boundary lubrication, in order to enhance tribochemical surface effects. The nature of tribofilms formed was studied by coupling high‐resolution TEM on wear fragments and inside‐wear‐scar, micro‐spot XPS in the same location of the wear track (so‐called dual analysis). The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS2 single sheets and the digestion of MoO3 in the zinc polyphosphate glass formed. The final result of the tribochemical reaction is a two‐phase tribofilm composed of (i) non‐oriented MoS2 sheets (friction modifier) embedded in a carbon‐rich phase and (ii) a mixed Zn/Mo polyphosphate glass (antiwear). The Modtc/OCB mixture has a similar antiwear mechanism except that the oxide is not completely eliminated, due to the softer action of borate anion compared with phosphate one. Compared to the data obtained with binary combinations (Modtc/Zndtp, Modtc/OCB and Zndtp/OCB), we show here that the ternary system Modtc/Zndtp/OCB provides both a low wear rate and an ultralow friction value, while adding detergent and anti‐corrosive properties to the formulation. Our analytical data indicate that the synergistic effect can be attributed to an outstanding nanostructure of the tribofilm formed. It is composed of a single‐phase material containing perfectly oriented MoS2 single sheets embedded in a calcium and zinc borophosphate glass. The ternary system produces a smart material in the interface, because both functions (antiwear and friction reduction) are correlated. Compared to phosphate alone, the mechanism by which MoS2 sheets have been oriented in the borophosphate could be related to aligned molecules of the glassy polymer in the direction of sliding.

Adhesion-related glycocalyx study: quantitative approach with imaging-spectrum in the energy filtering transmission electron microscope (EFTEM)

Large polysaccharide molecules composing the glycocalyx have been shown to prevent cell adhesion. However, this process was not observed microscopically. Terbium labeling, combined with a new quantitative imaging method based on electron energy loss spectroscopy, allowed specific glycocalyx staining with excellent contrast. Image analysis enabled us to compare glycocalyx structure in free membrane areas and contacts between monocytic cells and bound erythrocytes. Apparent glycocalyx thickness, in contact areas, was half of the sum of glycocalyx thicknesses in free areas without label density increase. Ultrastructural immunogold localization of CD43 molecules, a major component of glycocalyx, was also demonstrated to be excluded from contact areas during adhesion. Thus, both approaches strongly suggest that some glycocalyx elements must exit from contact to allow binding of adhesion molecules.

Superlow friction of ta-C lubricated by glycerol: An electron energy loss spectroscopy study

Energy-filtering transmission electron microscopy (EFTEM) analysis coupled with the technique of samples preparation, focused ion beam, was used to study physical, chemical, and mechanical properties of diamond-like carbon coatings (DLCs). Two different coatings (ta-C and a-C:H) were investigated, presenting different tribological behaviors in a boundary lubrication regime with glycerol. Electron energy loss spectroscopy appears to be a very powerful technique to characterize such DLC coatings. Special attention was paid to the maximum energy of the plasmon peak, which was used to evaluate some physical and mechanical properties of DLC coatings (density, sp3∕sp2 ratio, hardness). For ta-C superlubric coating, EFTEM results show a rearrangement of the DLC bulk structure under the friction process. Typically, the transformation of sp3 carbon into sp2 carbon was clearly observed and permits a self-adaptation of the coating, allowing it to support shearing without any delamination in spite of important compre...

Chemical bond mapping of carbon by image-spectrum EELS in the second derivative mode

Abstract Electron Energy-Loss Near Edge Structure (ELNES) mapping has been performed by using an energy-filtering TEM and the recently developed image-spectrum acquisition technique. The performance of the method in terms of spatial and energy resolution was evaluated by using a Zeiss 902 EFTEM and a specific software for this application. The experimental model was calcite material (CaCO3) deposited on a pure carbon film. This specimen contains two chemical bondings for carbon atoms, namely the CC and the CO bondings. Selected-area EELS spectra of the carbon K-edges showing the characteristic 1 s π ∗ transitions could be extracted from 8 nm diameter zones from series of energy-filtered images. The predicted change in the EELS spectrum of sp2 hybridised carbon K-edge due to a chemical shift is clearly visible. The mapping of the 1 s π ∗ (CC) molecular transition (peaking at 285 eV) was clearly distinguished from the 1 s σ ∗ (CO) one at 299 eV. For mapping the 1 s π ∗ (CO) at 291 eV as well as the 1 s s ∗ (CC) molecular transitions, a second derivative method was found to remove the background more correctly with the advantage to reduce the number of images (and therefore the dose). In the state of our knowledge, this represents the first molecular orbital mapping by EFTEM with a 256 × 256 image size where two chemical bondings of an element can be separated.

Tribochemistry: Friction-induced lamellar solids from lubricant additives

In this work, we have evidenced the formation of a lamellar solid from the tribochemical reaction of a borated additive and a succinimide additive. The result is the formation of h-BN in the tribofilm. The tribofilm is mainly composed of an amorphous borate matrix containing highly-dispersed h-BN nanoparticles in the form of sheets less than 10 nm wide and 5 nm thick. The originality of this h-BN tribochemical reaction lies in the nature of the intermolecular reaction between the two additives. At the opposite, MoS 2 formation from moDTC is the result of intramolecular chemical reaction.

Understanding the Deformation of Soot Particles/Agglomerates in a Dynamic Contact: TEM In Situ Compression and Shear Experiments

This work investigates the effect of compression and sliding on diesel soot in a confined space. Experiments were conducted in a high-resolution transmission electron microscope equipped with an in situ nanoindenter mounted with a truncated diamond tip to manipulate single soot particles and agglomerates. It was shown that both, agglomerates and single particles, were quite resistant to load. Agglomerates did not break during the compression tests; instead, partially reversible compaction of the particles to fill the free space was witnessed, proving that strong cohesive forces exist between the soot particles. The primary particles exhibited good elastic behavior under compression, and the agglomerates mirrored this behavior. Sliding tests have shown the ability of both the agglomerates and single primary particles to roll in the contact zone. This work showed that diesel soot is highly resilient to stress.