Understanding the Tribochemical Mechanisms of IF-MoS<Subscript>2</Subscript> Nanoparticles Under Boundary Lubrication

Inorganic fullerene-(IF)-like nanoparticles made of metal dichalcogenides (IF-MoS₂, IF-WS₂) have been known to be effective as anti-wear and friction modifier additives under boundary lubrication. The lubrication mechanism of these nanoparticles has been widely investigated in the past and it is now admitted that their lubrication properties are attributed to a gradual exfoliation of the external sheets of the particles during the friction process leading to their transfer onto the asperities of the reciprocating surfaces. However, the chemical interaction between these molecular sheets and the rubbing surfaces has so far never been investigated in detail. In this study, the tribochemistry of the IF nanoparticles was carefully investigated. A series of friction test experiments on different rubbing surfaces (Steel, Alumina, Diamond-Like Carbon) were performed with IF-MoS₂ nanoparticles. High-resolution transmission electron microscopy, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the tribostressed areas on rubbing surfaces. A tribofilm composed of hexagonal 2H-MoS₂ nanosheets was only observed on the steel surface. This transfer film was found to be incorporated into an iron oxide layer. A tribochemical reaction between the 2H-MoS₂ nanolayers and the iron/iron oxide has been proposed as an explanation for the adhesion of this tribofilm. The tribochemical mechanism of the IF-MoS₂ nanoparticles is discussed in this article.     

Nanotribology and lubrication mechanisms of inorganic fullerene-like MoS<Subscript>2</Subscript> nanoparticles investigated using lateral force microscopy (LFM)

Inorganic fullerene-like (IF) MoS₂ nanoparticles were produced by arc discharge in water, and their tribological properties were investigated using a lateral force microscope in dry nitrogen and humid air. Two types of tips – Si and Si₃N₄ tips were used in this work. The sharp Si tip produced a much higher contact stress than the blunt Si₃N₄ tip. The measurement of lateral forces using a Si₃N₄ tip resulted in almost no wear, while the measurement made using a Si tip resulted in MoS₂ transfer due to the high contact stress. For comparison, measurements were also made on MoS₂ films grown by pulsed laser deposition (PLD). The experimental results demonstrated that IF-MoS₂ nanoparticles had significantly lower friction than the MoS₂ films prepared by PLD. Variation of the test environment from dry to wet did not affect the tribological performance of the IF material as much as it did PLD films due to the chemical inert structure of the IF-MoS₂ nanoparticles. The multi-wall-encapsulated structure of inorganic fullerenes has a nearly isotropic geometry. They can supply a slippery surface in all orientations, though only the basal planes of 2H–MoS₂ crystals are optimum for lubrication. Therefore, the inorganic fullerenes do not have to be oriented by rubbing as does most layer-structured solid lubricants. However, the lack of reactive edge planes impedes bonding of the lubricant to the surface. The lubrication mechanisms of IF-MoS₂ nanoparticles are discussed in detail.     

In Situ TEM Observation of the Behavior of an Individual Fullerene-Like MoS<Subscript>2</Subscript> Nanoparticle in a Dynamic Contact

Inorganic fullerene-(IF)-like nanoparticles made of metal dichalcogenides (IF-MoS₂, IF-WS₂) have been known to be effective as anti-wear and friction modifier additives under boundary lubrication. The lubrication mechanism of these nanoparticles has been widely investigated in the past and even if the exfoliation and third body transfer of molecular sheets onto the asperities constitute the prevalent mechanism for the improved tribological behavior of IF nanoparticles, it has also been suggested that a rolling friction process could also play a role for well crystallized and spherical particles. In this study, in situ Transmission Electron Microscopy (TEM) observations of the behavior of single IF-MoS₂ nanoparticles were conducted using a sample holder that combines TEM and Atomic Force Microscopy (AFM) which simultaneously can apply normal and shear loads. It was shown that depending on the test conditions, either a rolling process or a sliding of the fullerenes could be possible. These in situ TEM observations are the first carried out with IF nanoparticles.     

Study on the Synthesis and Tribological Property of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Based Magnetic Fluids

In this paper, Fe₃O₄ based magnetic fluids with different particle concentrations were prepared by the co-precipitation technique. The size of the Fe₃O₄ nanoparticles is about 13 nm and their shape is spherical. The tribological performances of the fluids with different concentration Fe₃O₄ nanoparticles were evaluated in a MMW-1A four-ball machine. The results show that the tribological performance of magnetic fluids with proper Fe₃O₄ nanoparticles can be improved significantly. The maximum nonseized load (P _B) has been increased by 38.4% compared with carrier liquid. The wear scar diameter has been reduced from 0.68 mm to 0.53 mm and the relative percentage in friction coefficient has decreased to 31.3%. The optimal concentration of the Fe₃O₄ nanoparticles in the carrier liquid is about 4 wt.%.     

Synergistic Effect of Nano-MoS<Subscript>2</Subscript> and Anatase Nano-TiO<Subscript>2</Subscript> on the Lubrication Properties of MoS<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> Nano-Clusters

A MoS₃ precursor deposited on anatase nano-TiO₂ is heated at 450 °C in an H₂ atmosphere to synthesize MoS₂/TiO₂ nano-clusters. The nano-clusters are then characterized, and their tribological properties are evaluated. MoS₂ is found to be composed of layered structures with 1–10 nm thicknesses, 10–30 nm lengths, and 0.63–0.66 nm layer distances. The MoS₂ sizes in the MoS₂/TiO₂ nano-clusters are smaller and their layer distances are larger than those of pure nano-MoS₂. The MoS₂/TiO₂ nano-clusters also present a lower average friction coefficient than pure nano-MoS₂, but the anti-wear properties of both the nano-clusters and pure nano-MoS₂ are similar. X-ray photoelectron spectroscopy indicates that nano-TiO₂ and the element Mo are transferred to the friction surface from the MoS₂/TiO₂ nano-clusters through a tribochemical reaction. This produces a lubrication film containing TiO₂, MoO₃, and other chemicals. The nano-MoS₂ changes in size and layer distance when combined with nano-TiO₂, producing a synergistic effect. This may further be explained using a micro-cooperation model between MoS₂ nano-platelets and TiO₂ solid nanoparticles.     

Tribological behaviors and mechanisms of Ti<Subscript>3</Subscript>AlC<Subscript>2</Subscript>

Tribological behaviors and the relevant mechanism of a highly pure polycrystalline bulk Ti₃AlC₂ sliding dryly against a low carbon steel disk were investigated. The tribological tests were carried out using a block-on-disk type high-speed friction tester, at the sliding speeds of 20–60 m/s under a normal pressure of 0.8 MPa. The results showed that the friction coefficient is as low as 0.1∼0.14 and the wear rate of Ti₃AlC₂ is only (2.3–2.5) × 10⁻⁶ mm³/Nm in the sliding speed range of 20–60 m/s. Such unusual friction and wear properties were confirmed to be dependant dominantly upon the presence of a frictional oxide film consisting of amorphous Ti, Al, and Fe oxides on the friction surfaces. The oxide film is in a fused state during the sliding friction at a fused temperature of 238–324 °C, so it takes a significant self-lubricating effect.     

Tribological duality of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>

We report here on the friction behavior of fine- and coarse-grained Ti₃SiC₂ against steel and Si₃N₄ balls. Two successive friction regimes have been identified for both grain sizes and both counterparts. First, Type I regime is characterized by a relatively low (0.1–0.15) friction coefficient, and very little wear. Sliding occurs between a tribofilm on the ball and the Ti₃SiC₂ plane when against steel. Then, a Type II regime often follows, with increased friction coefficients (0.4–0.5) and significant wear. Compacted wear debris seems to act as a third body resulting in abrasion of the ball, even in the case of Si₃N₄. The transition between the two regimes occurs at different times, depending on various factors such as grain size, type of pin, and normal load applied. Some experiments under vacuum showed that the atmosphere plays also a major role. The reason for this evolution is not fully clear at that time, but its understanding is of major technological importance given the unusual good properties of this material.     

The Effect of Morphology on the Tribological Properties of MoS<Subscript>2</Subscript> in Liquid Paraffin

The tribological properties of liquid paraffin (LP) containing molybdenum disulfide (MoS₂) additives, including nano-balls, nano-slices, and bulk 2H-MoS₂, are evaluated using a four-ball tribometer. Results show that all MoS₂ additives used can improve the tribological properties of LP, and that nanosized MoS₂ particles function as lubrication additives in LP better than micro-MoS₂ particles do. The LP with nano-balls presents the best antifriction and antiwear properties at the MoS₂ content of 1.5 wt%. This is ascribed to the chemical stability of the layer-closed spherical structure of nano-balls. The Stribeck curves confirm that the rotation speed of 1,450 rpm used is located at the mixed lubrication region under 300 N. MoS₂ nano-slices have small sizes and easily enter into the interface of the friction pair with a roughness of 0.032 μm, functioning as a lubricant in LP better than nano-balls do at the MoS₂ content of 1.0 wt%. The Stribeck curves also show that the differences between the two nano samples were magnified at high rotation speeds in hydrodynamic lubrication region. The application of nano-slices in high sliding speeds will be more advantageous. This work furthers the understanding of the relationship between the tribological properties and morphology of MoS₂.     

Speed and Atmosphere Influences on Nanotribological Properties of NbSe<Subscript>2</Subscript>

Nanotribological properties of NbSe₂ are studied using an atomic friction force microscope. The friction force is measured as a function of normal load and scan speeds ranging from 10 nm s⁻¹ to 40 μm s⁻¹ under two atmospheres (air and argon). At low speed, no effect of atmosphere is noticed and a linear relationship between the friction and normal forces is observed leading to a friction coefficient close to 0.02 for both atmospheres. At high speed, the tip/surface contact obeys the JKR theory and the tribological properties are atmosphere dependent: the shear stress measured in air environment is three times lower than the one measured under argon atmosphere. A special attention is paid to interpret these results through numerical data obtained from a simple athermal model based on Tomlinson approach.     

Comparison of the efficiency of modification of SHMPE by nanofibers (C,Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and nanoparticles (Cu,SiO<Subscript>2</Subscript>) when obtaining antifriction composites

The effect of various nanofillers (nanofibers of Al₂O₃ and carbon, nanopowders of copper and SiO₂) on the physico-mechanical and tribotechnical properties of superhigh-molecular polyethylene is investigated. It is determined that the modification of superhigh-molecular polyethylene by nanofibers and nanoparticles within the limits of 0.1–05 wt % results in a substantial rise in its deformation-strength characteristics and a multifold increase in its tribotechnical characteristics. By the methods of X-ray structure analysis, infrared spectroscopy, and electron microscopy, it is shown that modification of the polymer by the mentioned nanofillers results in the formation of an ordered (lamellar) permolecular structure. It is revealed that nanofibers form a stable film of friction transfer more quickly in comparison with nanoparticles. The optimum compositions of nanofillers, which determine the high wear resistance and the low constant of friction for polymer, are determined. The mechanical activation of the binder and filler powders provides a uniform distribution of the nanopowder within the binder and additionally enhances the physico-mechanical and tribotechnical properties of the composite.     

Microstructure and Lubrication Properties of Lamellar Liquid Crystal in Brij30/[Bmim]PF<Subscript>6</Subscript>/H<Subscript>2</Subscript>O System

The microstructure of lamellar liquid crystal composed by nonionic surfactant polyoxyethylene laurylether (Brij30), room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF₆) and water is investigated by deuterium nuclear magnetic resonance (²H NMR) and rheological techniques. And the lubrication properties of the lamellar mesophase are determined to illustrate their relationship with the microstructure. The results show that the structure strength of the lamellar phase is enhanced with increasing amount of Brij30, so the anti-wear capacity of the lamellar phase is improved. But, both of the structure strength and lubrication properties are impaired with increasing water content in the system due to the increased interlayer space and the penetration of water into the amphiphile bilayer. However, though the structure of the lamellar phase is disturbed by [Bmim]PF₆, the lubrication properties are still improved due to the inherent lubrication properties of [Bmim]PF₆.     

Friction and wear of fullerene-like WS<Subscript>2</Subscript> under severe contact conditions: friction of ceramic materials

Recently, the behavior of inorganic fullerene-like (IF) WS₂ nanoparticles in the interface of steel-on-steel pair has been analyzed. It was shown that originally when the gap between the contact surfaces is smaller than the size of the IF nanoparticles, there is no effect of the nanoparticles on the friction force. During the test stiff IF nanoparticles can plough the surface of hard steel samples and penetrate into the interface under friction. Molecular sheets of WS₂ from the delaminated IF nanoparticles, which reside in the valleys of the rough surfaces cover the contact spots and thus decrease the number of adhered spots at the transition to seizure. The goal of the present work was to study the behavior of IF nanoparticles in the interface of ceramic surfaces. The friction tests were performed using a ball-on-flat device. A silicon nitride ball was slid against an alumina flat with maximum contact pressure close to 2 GPa. SEM, TEM and AFM techniques have been used in order to assess the behavior of IF nanoparticles in the interface. The behavior of IF nanoparticles in the much harder ceramic interfaces was found to be appreciably different from the steel pair. The pristine IF nanoparticles are damaged in the inlet of the contact during the first few cycles and thin shells of broken nanoparticles gradually cover the middle range of the contact surface. Different modes of deformation and destruction of the IF nanoparticles are exhibited when going from the middle to edge area of the contact. While aggregates of the pristine nanoparticles are formed at the edge of the contact, thin shells of broken IF nanoparticles are observed in the middle area where contact pressure is maximum. Mechanical stability and damage of IF nanoparticles in the ceramic interface are discussed.     

Tribological Properties of CaCO<Subscript>3</Subscript> Nanoparticles as an Additive in Lithium Grease

CaCO₃ nanoparticles with an average size of 45 nm were synthesized via the carbonation method. The tribological properties of the CaCO₃ nanoparticles as an additive in lithium grease were evaluated with a four-ball tester. The results show that these CaCO₃ nanoparticles exhibit good performance in anti-wear and friction-reduction, load-carrying capacity, and extreme pressure properties. The action mechanism was estimated through analysis of the worn surface with X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). The results indicate that a boundary film mainly composed of CaCO₃, CaO, iron oxide, and other organic compounds was formed on the worn surface during the friction process.     

Correlation Studies of WS 2 Fullerene-Like Nanoparticles Enhanced Tribofilms: A Scanning Electron Microscopy Analysis

The beneficiary effects of tungsten disulphide (WS₂) inorganic fullerene-like nanoparticles (IFLNPs) in the lubrication industry were shown in recent years. However, their successful incorporation into lubricants (oils, greases) is not straightforward. In practice, the lubricant contains several components for different purposes, e.g. reducing the oxidization of the oil (antioxidant), minimizing the wear rate (anti-wear additive), dispersants, etc. These additives can contain chemically active compounds, which under the lubrication process (where locally extreme conditions can develop: high pressure and flash temperatures) can change the chemistry in the contact zone and block the beneficial effects of the inorganic nanoparticles. In this investigation, poly-alpha-olefin (PAO) is being used as base oil in which the WS₂ nanoparticles and different additives are mixed. A ball-on-disc sliding test revealed that certain additives inhibit the nanoparticles to reduce friction (less than 5 % decrease in friction coefficient), while in other cases, the friction reduction was above 50 %. The comparison is being made between PAO + additive and PAO + additive + IFLNPs. Scanning electron microscope and energy dispersive X-ray spectroscopy were used to investigate the elemental composition of the tribofilms formed on the wear marks. Further analysis was made in order to reveal correlations between elemental compositions of the tribofilms and external parameters such as the friction coefficient and wear rate. For instance, a strong correlation between tungsten content of the tribofilm and the friction coefficient was found.     

Tribological behaviour of MoS2 and inorganic fullerene-like WS2 nanoparticles under boundary and mixed lubrication regimes

Abstract

For several years different types of nanoparticles have been considered and studied as potential friction modifying lubricant additives. Some nanoparticles can reduce the friction coefficient by 30–70%, depending on the base oil and the experimental conditions. In the present study, an experimental analysis on tribological properties of inorganic fullerene-like metal dichalcogenides was performed in comparison with MoS₂ 2H layered structures. Tribological tests were carried out on a pin on disc tribometer in ambient air. Several contact conditions are analysed in order to realise boundary and mixed lubrication regimes. The experimental study was performed on a mineral base oil, and particle concentration effects were analysed. Antifriction properties were evaluated by measuring the friction coefficient and are presented as generalised Stribeck diagrams. Inorganic fullerene-like WS₂ and MoS₂ nanoparticles present interesting friction reduction properties when tested in boundary and mixed lubrication.     

The Effect of WS2 Nanoparticles on Friction Reduction in Various Lubrication Regimes

A study of the tribological behavior of nested inorganic fullerene-like (IF) nanoparticles of WS₂, as a potential additive to base oils is presented. Friction measurement results obtained from three different test rigs over a wide range of normal loads and sliding velocities are shown. Stribeck curves are used to reveal the lubrication regimes where the IF are most effective. It is found that the addition of IF-WS₂ nanoparticles to the base oils results in up to 50% reduction in friction coefficient in the mixed lubrication regime. The mechanism of improved friction and wear behavior with the IF additive is discussed.     

Direct visualization of sliding-induced tribofilm on Au/MoS<Subscript>2</Subscript> nanocomposite coatings by c-AFM

The nanoscale lubrication mechanism of nanocomposite Au/MoS₂ solid lubricant coatings has been studied by conductive atomic force microscopy (c-AFM). A direct visualization of the lubricating process suggests tribomechanical formation of a MoS₂ tribofilm to be a key mechanism. The sliding-induced tribofilm formation was visualized by a reduction in local friction and conductivity in nanoscale AFM images. The tribofilm was found to possess considerable crystallinity and orientation, which was not observed in the as-deposited coatings. The observed mechanism is broadly applicable to a range of nanocomposite metal/MoS₂ coatings.     

Antispalling Effect of WS2 Nanoparticles on the Lubrication of Automotive Gearboxes

The effect of WS₂ nanoparticles used as lubricant additives in the lubrication of automotive gearboxes has been studied. The results suggest that nanoparticles can be used to increase the life span of the mechanical parts of gears. Chemical analyses and observations made after transmission tests have shown that nanoparticles are able to go inside cracks and may have a sealing effect, preventing spalling and further failure of the material. Moreover, the addition of nanoparticles in fully formulated oil reinforces the antispalling properties of the lubricant.     

Tribological studies of rhenium doped fullerene-like MoS2 nanoparticles in boundary,mixed and elasto-hydrodynamic lubrication conditions

The tribological properties of rhenium-doped inorganic fullerene-like MoS₂ nanoparticles were studied in poly alpha olefin oil, and compared to inorganic fullerene-like (IF) MS₂ (M=Mo,W) nanoparticles and 2H-MoS₂ platelets. For this purpose a rotational disc tribometer was used. Different regimes in the Stribeck curve, i.e., boundary, mixed and elasto-hydrodynamic lubrication conditions were studied. A precipitous reduction in friction and wear of oil suspensions with nanoparticles were observed for the entire IF samples. However, Re-doped IF exhibited the best results, presumably due to their reduced tribocharging and agglomeration. The various tribological mechanisms of solid state additives are discussed.     

Fullerene-like MoS<Subscript>2</Subscript> Nanoparticles and Their Tribological Behavior

Using a new quartz-made reactor, large amounts of fullerene-like (IF) MoS₂ nanoparticles were synthesized by reacting MoO₃ vapor with H₂S in a reducing atmosphere. The nanoparticles were found to be of high crystalline order; with an average size of 70 nm and consist of more than 30 closed shells. Extensive tribological testing of the nanoparticles in two types of synthetic oils- poly-alpha olefins (PAO)- was carried out and compared to that of bulk (2H platelets) MoS₂ and IF-WS₂. These tests indicated that under high pressure and relatively low humidity, the IF-MoS₂ exhibited a friction coefficient as low as 0.03 and the smallest wear rate of the measured systems. However, its performance was found to be lower in comparison to IF-WS₂ after 2500 cycles, due probably to its inferior chemical stability. This study indicates that the tribological performance of the IF nanoparticles depends strongly on their crystalline order and size.