Direct observation by in situ transmission electron microscopy of the behaviour of IF‐MoS2 nanoparticles during sliding tests: influence of the crystal structure

Direct observation of the behaviour of individual inorganic fullerenes (IF)‐MoS₂ nanoparticles in a sliding interface is essential for the understanding of the influence of the intrinsic characteristics of the nanoparticles on their lubrication mechanisms, when they are used as additives in lubricant oil. In this work, in situ transmission electron microscopy sliding tests were performed on two different types of MoS₂ nanoparticles synthesised by two different methods. It is shown that the IF‐MoS₂ nanoparticles having perfect structure with a high crystalline order and without defects are able to roll and to slide under the combined effect of pressure and shear stress, whereas the IF‐MoS₂ nanoparticles containing many defects exfoliate immediately in the same conditions to deliver MoS₂ layers covering the mating surfaces. A link between these results, the lubrication mechanisms of the nanoparticles and their tribological properties at the macro‐scale was established, proving that the lubrication mechanisms of fullerenes depend on their intrinsic characteristics. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

On the Efficacy of IF–WS<Subscript>2</Subscript> Nanoparticles as Solid Lubricant: The Effect of the Loading Scheme

Fullerene-like WS₂ (MoS₂) nanoparticles (IF) have been studied in the past as solid lubricants. Using the tribological ball-on-flat experiments, it was shown that the size of the aggregates and their distribution determine the penetration and entrapping of the IF nanoparticles at the interface. It is expected that the wedge clearance at the inlet of the contact, i.e., the oblique-angle entrance to the contact zone between the two mating tribological surfaces, as well as the average surface roughness, can limit the supply of the lubricant into the interface in, e.g., the block-on-ring experiment. In the present series of experiments, the Stribeck curve was designed first using a linear loading scheme and pure oil. It was concluded that a wedge clearance (oblique-angle) in the inlet of the contact zone leads to entrapment of the IF nanoparticles and their compaction, which hamper the supply of the fluid lubricant into the interface. A ball-on-flat and flat block-on-ring friction devices with wedge clearance in the inlet of the contact can distort the efficacy of IF. Procedures for improving the supply of the IF nanoparticles to the contact zone and improving thereby their efficacy are considered.     

Sedimentation of IF-WS2 aggregates and a reproducibility of the tribological data

Inorganic fullerene-like (IF) solid lubricant nanoparticles and nanotubes with extremely useful mechanical and tribological characteristics have been realized, offering a plethora of new applications for these nanomaterials. The IF nanoparticles were found to be in the aggregated state. It is expected that the size of the aggregates and their distribution determine the penetration and entrapping of IF nanopowder into the interface. The main goal of the present work is to elucidate the effect of the mixing time of IF-WS₂ nanomaterial in the oil on the size of the IF aggregates and their influence on the friction and wear. The fraction of small aggregates increases and that of the large aggregates decreases with longer mixing time. Consequently, the spread of the tribological results diminishes with the lengthening of the mixing time.The reproducibility of the friction results for the pairs lubricated with oil +IF nanoparticles is determined by distribution of the IF aggregates in the lubricant and the size of the solid lubricant aggregates.     

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.     

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.     

High Lubricity of Re-Doped Fullerene-Like MoS2 Nanoparticles

The electrostatic effects in tribological systems have been studied in the past, especially with regards to data storage media. Nanoparticles (NP) of WS₂ and MoS₂ with fullerene-like structure (IF) have been studied in the past and showed very good tribological behavior. Being semiconductors, their electrical properties can be controlled by, e.g., substituting the lattice Mo (W) atoms with Re (n-type conductivity) and Nb (p-type conductivity) atoms. In this study doping of IF-MoS₂, and to a lesser degree IF-WS₂, NP with small amounts (< 1 at.%) of rhenium atoms has been studied. For this purpose two new synthetic approaches have been pursued. The doped nanoparticles were characterized by various techniques. In particular, the doping density was determined by ICP-MS technique. The resistivity of the nanoparticles was shown to decrease significantly with increasing doping level. In contrast to the undoped nanoparticles, the doped NP were shown to exhibit reduced agglomeration and produce stable suspensions in PAO-4 and PAO-6 oils. Extensive tribological measurements with these PAO oils formulated with 1 wt % of the doped NP showed friction coefficients as low as 0.01 in mixed lubrication conditions and negligible wear. Microscopy analysis of the tribological surfaces reveal very smooth but discontinuous and dense film of the doped NP on the tribological surfaces. It is proposed that the doped NP are negatively charged at their surface eliciting mutual repulsion, which has a remarkable influence on their rheological properties and their tribological behavior.     

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.     

A Raman Spectroscopic Study of MoS<Subscript>2</Subscript> and MoO<Subscript>3</Subscript>: Applications to Tribological Systems

Molybdenum disulfide (MoS₂) and molybdenum trioxide are investigated using Raman spectroscopy with emphasis on the application to tribological systems. The Raman vibrational modes were investigated for excitation wavelengths at 632.8 and 488 nm using both micro-crystalline MoS₂ powder and natural MoS₂ crystals. Differences are noted in the Raman spectra for these two different wavelengths, which are attributed to resonance effects due to overlap of the 632.8 nm source with electronic absorption bands. In addition, significant laser intensity effects are found that result in laser-induced transformation of MoS₂ to MoO₃. Finally, the transformation to molybdenum trioxide is explored as a function of temperature and atmosphere, revealing an apparent transformation at 375 K in the presence of oxygen. Overall, Raman spectroscopy is an useful tool for tribological study of MoS₂ coatings, including the role of molybdenum trioxide transformations, although careful attention must be given to the laser excitation parameters (both wavelength and intensity) when interpreting Raman spectra.     

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.     

Effect of Atmosphere and Temperature on the Tribological Behavior of the Ti Containing MoS<Subscript>2</Subscript> Coatings Against Aluminum

MoS₂ coatings exhibit low coefficient of friction (COF) when sliding against aluminum; however, the magnitudes of their COF show high sensitivity to environmental conditions. Ti could reduce the sensitivity of the frictional behavior of MoS₂ coatings to moisture. This study examines the tribological properties of Ti containing MoS₂ coating (Ti–MoS₂) tested against an aluminum alloy (Al-6.5% Si) in ambient air (58% relative humidity, RH), dry oxygen, dry air and dry N₂ (< 4% RH) atmospheres. The Ti–MoS₂ coating exhibited similar COF values under an ambient (0.14), dry oxygen (0.15) and dry air (0.16) atmospheres. It was found that oxidation of MoS₂ to MoO₃ was responsible for high COF under these testing conditions as revealed by Energy-dispersive X-ray Spectroscopy (EDS) and micro-Raman spectroscopy. However, a low and stable COF of 0.07 was observed under a dry N₂ condition. This work further showed that the tests performed at elevated temperatures, up to 400 °C in a dry N₂ atmosphere sustained the low and stable COF of the Ti–MoS₂ coatings. The sliding tests performed under a dry N₂ atmosphere prevented the formation of MoO₃ and as a result, the Ti–MoS₂ coatings maintained low COF values. Low COF values were also attributed to the formation of MoS₂ transfer layers.     

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.     

A new way to feed nanoparticles to friction interfaces

Fullerene-like WS₂ (MoS₂) nanoparticles (IF) have been studied in the past. Their efficacy as additives for lubrication fluids has been demonstrated. It was shown that the IF nanoparticles are usually delaminated in the inlet of the smooth contact. Thin sheets of broken IF nanoparticles can be entrapped between the rubbed surfaces and thus favorably affect the friction and the wear. Friction pairs at real mechanical macrosystems are often subjected to friction-induced vibrations. It was shown that the mechanical excitations can improve the supplying and preservation of fluid lubricant film in the interface. It can be hypothesized that under vibrations in a definite range of frequencies and amplitudes, the probability for small IF aggregates to be entrapped into the interface is increased. The main goal of this work was to study the effect of artificial mechanical excitations on the friction and wear of contact pairs rubbed with nanoparticles. In order to avoid friction-induced excitations, a new ball-on-flat friction device was developed. The frequency and the amplitude of the ball were varied using a motion of miniature micromotor attached to the ball holder. The behavior of IF nanoparticles in friction tests with and without external mechanical excitations was compared with the tribological behavior of the contact pair lubricated with pure paraffin oil. It was found that the external mechanical excitation of the mechanical parts rubbed with nanoparticles allows a penetration of these nanoparticles into interface. This effect leads to a remarkable shortening of the run-in period and improves the tribological properties of contact pairs. From the present results it may be anticipated that the accidental friction-induced vibrations, which are determined by the stiffness and damping force of the device, lead to preferential penetration of the IF nanoparticles into the contact area, affecting thereby the tribological behavior of the interface.     

Frictional Characteristics of IF-WS2 Nanoparticles in Simulated Engine Conditions

The efficacy of inorganic fullerene-like (IF) tungsten disulfide (WS₂) nanoparticles as engine oil friction modifier additive was investigated using a high-stroke reciprocating piston ring–cylinder bore bench test system. Frictional characteristics of various IF-WS₂ nanoparticle concentrations in mineral oil were experimentally analyzed in simulated engine conditions controlling oil temperature, speed, and normal load. Though the effect of IF-WS₂ nanoparticles on piston ring and cylinder bore friction was minor in low concentrations, after a running period in a mixed lubrication regime with 10% additive, a considerable reduction in friction coefficient was observed when the IF-WS₂ formulated oil was used. This reduction remains to some extent with reference mineral oil after solvent cleaning of the mating components. The results show that a thin tribofilm gradually forms on the piston ring and the cylinder bore surfaces, reducing the friction coefficient in a mixed lubrication regime. However, in order to obtain the friction reduction there seems to be a threshold in the concentration of IF-WS₂ in mineral oil and film development period. The effects of lubrication regime, contact load, speed, and surface roughness on tribofilm formation are also discussed. The presence of WS₂ tribofilm formed on the piston ring and the cylinder bore surfaces was further verified using Raman spectroscopy.     

Various MoS2-, WS2- and C-Based Micro- and Nanoparticles in Boundary Lubrication

Various solid lubricant particles have been experimentally evaluated as possible additives to oils. However, information in terms of a direct comparison of their tribological properties is still missing. In this study, we have compared the tribological properties of seven different solid lubricant micro- and nanoparticles as additives in polyalphaolefin (PAO) oil: MoS₂ nanotubes, MoS₂ platelets (2 and 10 μm), WS₂ nanotubes, WS₂ fullerene-like nanoparticles, graphite platelets (20 μm) and multi-walled carbon nanotubes. The experiments were performed in the boundary lubrication regime under a contact pressure of 1 GPa (Hertz, max) using a ball-on-disc tribotester. In general, the particles significantly decreased the friction and wear compared to the base PAO oil. We found that it was the material of the particles that largely determined their tribological performance. The effect of the size of the particles was much less important, and the morphology (shape) of the particles had little or no influence. We have also investigated the effect of ultrasonication during suspension preparation on particle damage and found that the solid lubricant particles were not notably affected, except the MoS₂ and WS₂ nanotubes, which became somewhat shorter.     

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.     

The Tribological Mechanism of MoS<Subscript>2</Subscript> Film under Different Humidity

Molybdenum disulfide (MoS₂) has been widely used in vacuum environment as an excellent solid lubricant. However, the application of MoS₂ is greatly limited in terrestrial atmosphere due to the sensitivity to humidity. Although the sensitivity of MoS₂ to water vapor has been widely recognized, the mechanism is not clear. To explore the tribological mechanism of MoS₂ in the presence of water vapor, a series of experiments were performed to investigate the effect of N₂ (inert gas), O₂ (active gas), air (a combination of both) and cyclic humidity change in air on the frictional response of MoS₂ to humidity. According to the results, a model that described water adsorption enhanced by active sites in MoS₂ and formed oxides, and an adsorption action change in water molecules with humidity was proposed. The model was applied to explain the recovery and instantaneous response of friction coefficient to humidity change.     

Synthesis and Tribological Performance of Novel MoxW1?xS2 (0?≤?x?≤?1) Inorganic Fullerenes

Inorganic fullerene-like (IF) MoS₂ and WS₂ nanoparticles were found to be good friction modifiers and anti-wear additives when dispersed in a lubricant. Their tribological performance seems to be related to the structure, size, and shape of these nanomaterials. The present study describes the tribological properties of a new inorganic fullerene IF-Mo _x W_1−x S₂ containing both molybdenum and tungsten disulfide under boundary lubrication. Mo _x W_1−x S₂ amorphous inorganic fullerene nanostructures were synthesized by means of MOCVD using an induction furnace setup. The average diameters range from 25 to 45 nm. Upon variation of the amounts of precursors and S, various solid solutions of IF-Mo _x W_1−x S₂ were obtained. In addition, a morphological, chemical, and structural analysis of the samples was performed using high resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), and X-ray powder diffraction (XRD). Friction experiments were carried out with a ball-on-flat contact using an environmental tribometer. The results show interesting friction reducing and wear properties of these nanomaterials. The change in the molecule stoichiometry, which led to a variation of particles size but also to a variation of the crystallinity of the particles, affects the tribological performance.