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.     

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.     

MoS<Subscript>2</Subscript> Films Formed by <Emphasis Type="Italic">In-contact</Emphasis> Decomposition of Water-soluble Tetraalkylammonium Thiomolybdates

Synthesis and tribological evaluation of three tetraalkylammonium thiomolybdate (R₄N)₂MoS₄ (R = methyl, propyl, or ammonia) aqueous-based lubricant additives on a ball-on-disk tribometer was carried out for a steel–aluminum contact. Tests were performed at the same conditions of load, entrainment speed, sliding distance, temperature, and concentration of MoS₂ to compare the activity (lubrication effect) of the thiomolybdates prepared. A friction reduction is observed for the three salts compared to pure water; however, significant differences in friction coefficient are observed depending on the alkyl group. SEM/EDAX and Raman analysis of the wear tracks reveal the in-contact formation of a MoS₂-lubricating film, rich in molybdenum and sulfur.     

Effect of deposition pressure on microstructure and tribological behavior of MoS<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/MoS<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-Mo nanoscale multi-layer films

MoS _x /MoS _x -Mo multi-layer films consisted of several bilayers and a surface layer on steel substrate were deposited by d.c. magnetron sputtering at different deposition pressures. Each bilayer contained a MoS _x layer with 80 nm in thickness and a MoS _x -Mo composite layer with 20 nm in thickness. With the increase of deposition pressure, the perpendicular orientation of the basal plane prevailed while the parallel orientation decreased. The tribological properties of the multi-layer films were investigated by using a ball-on-disk tribometer both in vacuum and in humid air. The multi-layer film deposited at 0.24 Pa had a compact, consistent layered structure with high intensity of (002) plane and low S content compared to the others deposited at 0.32 and 0.40 Pa, and showed the lowest friction coefficient and wear rate in humid air.     

Multi-environmental lubrication performance and lubrication mechanism of MoS2/Sb2O3/C composite films

MoS₂–Sb₂O₃–C composite films exhibit adaptive behavior, where surface chemistry changes with environment to maintain the good friction and wear characteristics. In previous work on nanocomposite coatings grown by PVD, this type of material was called a “chameleon” coating. Coatings used in this report were applied by burnishing mixed powders of MoS₂, Sb₂O₃ and graphite. The solid lubricant MoS₂ and graphite were selected to lubricate over a wide and complementary range including vacuum, dry air and humid air. Sb₂O₃ was used as a dopant because it acts synergistically with MoS₂, improving friction and wear properties. The MoS₂–Sb₂O₃–C composite films showed lower friction and longer wear life than either single component MoS₂ or C film in humid air. Very or even super low friction and long wear-life were observed in dry nitrogen and vacuum. The excellent tribological performance was verified and repeated in cycles between humid air and dry nitrogen. The formation of tribo-films at rubbing contacts was studied to identify the lubricating chemistry and microstructure, which varied with environmental conditions. Micro-Raman spectroscopy and Auger electron spectroscopy (AES) were used to determine surface chemistry, while scanning electron microscopy and transmission electron microscopy were used for microstructural analysis. The tribological improvement and lubrication mechanism of MoS₂–Sb₂O₃–C composite films were caused by enrichment of the active lubricant at the contact surface, alignment of the crystal orientation of the lubricant grains, and enrichment of the non lubricant materials below the surface. Sb₂O₃, which is not lubricious, was covered by the active lubricants (MoS₂ – dry, C – humid air). Clearly, the dynamics of friction during environmental cycling cleaned some Sb₂O₃ particles of one lubricant and coated it with the active lubricant for the specific environment. Mechanisms of lubrication and the role of the different materials will be 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.     

Environmental Effects on the Tribology and Microstructure of MoS<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–C Films

The tribology of molybdenum disulfide (MoS₂)–Sb₂O₃–C films was tested under a variety of environmental conditions (ambient 50% RH, 10⁻⁷ Torr vacuum, 150 Torr oxygen, and 8 Torr water) and correlated with the composition of the surface composition expressed while sliding. High friction and low friction modes of behavior were detected. The lowest coefficient of friction, 0.06, was achieved under vacuum, while sliding in 8 Torr water and ambient conditions both yielded the highest value of 0.15. Water vapor was determined to be the environmental species responsible for high friction performance. XPS evaluations revealed a preferential expression of MoS₂ at the surface of wear tracks produced under vacuum and an increase in Sb₂O₃ concentration in wear tracks produced in ambient air (50% RH). In addition, wear tracks produced by sliding in vacuum exhibited the lowest surface roughness as compared to those produced in other environments, consistent with the picture of low friction originating from well-ordered MoS₂ layers produced through sliding in vacuum.     

Tribological characteristics of magnetron sputtered MoS2 films in various atmospheric conditions

The friction and wear behaviors of magnetron sputtered MoS₂ films were investigated through the use of a pin and disk type tester. The experiments were performed for two kinds of specimens (ground (Ra 0.5μm) and polished (Ra 0.01 μm) substrates) under the following operating condifions: linear sliding velocities in the range of 22 -66 mm/s(3 types), normal loads varying from 9.8-29.4 N(3 types) and atmospheric conditions of air, medium and high vacuum(3 types). Silicon nitride pin was used as the lower specimen and magnetron sputtered MoS₂ on bearing steel disk was used as the upper specimen. The results showed that low friction property of the MoS₂ films could be identified in high vacuum and the specific wear rate in air was much higher than that in medium and high vacuum due to severe oxidation. It was found that the main wear mechanism in air was oxidation whereas in high vacuum accumulation of plastic flow and adhesion, were the main causes of wear.     

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.     

Wear and frictional behaviour of MoS2 pellets and steel lubricated with MoS2 powder

The wear and frictional behaviour of compressed pellets of molybdenum disulphide (MoS₂) were measured when the pellets were slid against a 0.45% C steel disk in air. The wear of the MoS₂ pellets decreased with increasing sliding velocity and increasing contact pressure. These factors are indicated by a parameter μPV which corresponds to the frictional heat. A thin deformed surface layer on the sliding surface of an MoS₂ pellet was different from the MoS₂ substrate.The wear of a bearing steel slider against mild steel was reduced by an MoS₂ film in air and in vacuum. The specific wear rate of the slider and the coefficient of friction were influenced by the degree of vacuum.     

Friction and endurance of MoS2/ta-C coatings produced by Laser Arc deposition

The tribological behaviour of MoS₂/ta-C double layer coatings deposited by Laser-Arc technology was investigated in vacuum and air. In vacuum environment, the friction coefficient against steel balls varies between 0.005 and 0.02 depending on the contact pressure. At high contact pressures, the friction coefficient is as low as 0.005 and the life time between 340,000 and 500,000 cycles. Furthermore, it is shown that a ta-C base layer improves the performance of MoS₂ coating.Surface analyses were performed before and after the tribological tests by means of SEM, EDX, XRD, and TEM. They show that in the top layer beneath the sliding surface crystallization of the initially quasi-amorphous MoS₂ took place. TEM images also verified an orientation of the basal MoS₂-lattice planes parallel to the surface.     

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.     

Surface Engineering Design of Alumina/Molybdenum Fibrous Monolithic Ceramic to Achieve Excellent Lubrication in a High Vacuum Environment

Al₂O₃/Mo fibrous monolithic ceramics are potential candidates for space applications because of their excellent mechanical properties and low density. This study aims at achieving low friction and long life of this material in a high vacuum environment. Three-dimensional composite-lubricating layers were fabricated by considering texture pattern as storage dimples and MoS₂ synthesized via hydrothermal method as lubricant. The tribological properties were studied sliding against Si₃N₄ ceramic and GCr15 bearing steel balls under high vacuum condition. Results showed that the lubricating properties of the Al₂O₃/Mo fibrous monolithic ceramics were improved greatly by the micro-texture and MoS₂ solid lubricant; the friction coefficients were as low as approximately 0.08 and 0.04, respectively, when Si₃N₄ ceramic and GCr15 bearing steel balls acted as the pairing materials. It was also demonstrated that the low friction coefficient can be realized with various normal loads and sliding speeds, indicating the composite-lubricating layers have good adaptation of working conditions. This excellent performance of the material is mainly because of MoS₂ stored in dimples can be easily dragged onto the friction surface to form lubricating and transferring films during the friction process. This work is an extension of studies that were previously published in Tribology Letters journal.     

MoS2‐based alloys and nanocomposites for solid lubrication

The development of MoS₂ coatings has involved the modification of substrate surfaces, the addition of metals or compounds to the MoS₂, and variation in the deposition process parameters affecting the properties of deposited films. More recently, multilayer and periodic nanolayer coating structures have also been investigated. At present, work is concentrated on alloys of MoS₂, mainly with various metals, and targeted at terrestrial (ambient air) applications. The addition of metals or compounds to physical‐vapour‐deposited MoS₂ has led to improvements in coating performance, for example, greater stability of friction coefficient, greater film endurance, and increased temperature/oxidation resistance. The metal or compound can be either in the form of nanoscale multilayers or mixed with the MoS₂, sometimes leading to nanoclusters within a MoS₂ matrix. Microstructural analysis seems to show that the primary function of these additives is to suppress the formation of low‐density, columnar structures. At certain concentrations an added metal can also enhance the formation of the tribologically favourable (002) orientation of the MoS₂ crystallites. Other changes in the properties of MoS₂—metal composites may be due to their oxidation resistance, as indicated by the stability of these films against storage in air and their increased endurance when in sliding contacts at elevated temperatures.     

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.     

In Situ Analysis of Third Body Contributions to Sliding Friction of a Pb–Mo–S Coating in Dry and Humid Air

Reciprocating sliding tests of ion-beam deposited (IBD) Pb–Mo–S coatings were performed with an in situ tribometer that allows real-time visualization and Raman analysis of the sliding contact through a transparent hemisphere. Experiments were performed in dry air, ambient air (∼50% RH) and mixtures of dry and humid air cycled between low and high humidity. Third bodies formed in the sliding contact were monitored through an optical microscope and analyzed by Raman Spectroscopy. Third body velocity accommodation modes were identified and correlated with friction behavior in dry and ambient air. The dominant velocity accommodation mode in both dry and humid air was interfacial sliding between the outer surface of the transfer film and the wear track; this interface, based on present and earlier studies, is crystalline MoS₂. Therefore, the friction coefficient was controlled by the interfacial shear strength of MoS₂ sliding against MoS₂. Humid air sliding was accompanied by a rise in the friction coefficient and a small but observable second velocity accommodation mode: shear/extrusion of the transfer film. It is concluded that the friction rise in humid air was due to an increase in the interfacial shear strength, and that the rise in friction caused the third body to deform rather than the deformation causing the friction to rise.     

Lubrication at 750°C in a vacuum by a transfer film from self‐lubricating composites for roll/slide contact of Si3N4

Roll/slide friction tests were carried out at a temperature of 750°C in a vacuum. Disc specimens were made of Si₃N₄ with or without a sputtered MoS₂ film. A pin specimen was rubbed against one disc to supply a lubricating transfer film. With a pin made of an MoS₂‐based composite, the friction coefficient was around 0.3 and almost no wear of the discs was observed after 24 h of operation at a load of 50 N, a rotating speed of 0.5 m/s, and a slip ratio of 10%. Transferred patchy MoS₂ films were observed on the friction track. With a pin made of Ni‐based composite containing BN and graphite, the friction coefficient increased from 0.2 to 0.7 over a test time of about 8 h and severe disc wear was found. In an additional test using Si₃N₄ discs with a sputtered MoS₂ film without a pin, the friction coefficient was about 0.3, and no wear of the discs was found after 24 h of operation. The appearance of the friction track was similar to that in the test using the MoS₂‐based composite pin. It seems that the sputtered MoS₂ film wore, but wear particles reattached on the friction path to develop an effective lubricating film. These results demonstrate the effectiveness of transfer film lubrication for long‐term operation in a high‐temperature vacuum, and the superior ability of MoS₂ to develop an effective transfer film.     

Friction and Wear Properties of IF–MoS2 as Additive in Paraffin Oil

Inorganic fullerene-like (IF) MoS₂ nanoparticles with diameters ranging from 70 to 120 nm were synthesized by desulphurizing the MoS₃ precursor and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tribological properties of the IF–MoS₂, as lubricating oil additive, were evaluated using a MMW-1 four-ball tribotester. The wear scar was examined with an optical microscope and scanning electron microscopy (SEM). The wear resistance of the paraffin oil was improved and the friction coefficient of the oil was decreased by addition of the IF–MoS₂ nanoparticles. The mechanism of friction and wear of the IF–MoS₂ nanoparticles was 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.