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.     

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.     

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.     

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.     

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.     

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.     

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.     

On the possibility of improving antifriction properties of MoS<Subscript>2</Subscript> coatings by alloying

The paper presents an explanation of the improved antifriction properties of MoS₂ in vacuum compared to their properties in air. It is shown that the effect of superlow friction upon intensive irradiation results from the formation of a “two-dimensional gas” consisting of sulfur atoms knocked out of their positions. The possibility of the alloying of MoS₂ by elements which do not react with sulfur is analyzed. The alloying of MoS₂ coatings by an excess number of sulfur atoms to realize the effect of superlow friction in vacuum and air is substantiated.     

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.     

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.     

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.     

Tribological Properties of Nanocomposite CrC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/a-C:H Thin Films

Recently we showed that coatings, prepared by unbalanced magnetron sputtering from a metallic Cr target in an Ar/CH₄ discharge are composed of nanocrystalline CrC _x embedded in an a-C:H matrix. This work investigates the structural correlation of such nanocomposite CrC _x /a-C:H coatings to their tribological properties. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the phase composition and the chemical bonding in the films deposited at different experimental conditions. The coating microstructure was investigated on selected samples by high-resolution transmission electron microscopy. For CrC _x -dominated coatings deposited at CH₄ partial to total pressure ratios (p_CH4/p_t) < 0.42, only minor changes regarding the friction coefficients and the abrasive wear rates were observed although microstructural changes towards a higher degree of crystallinity were proven by transmission electron microscopy and substantiated with XPS results. For a-C:H dominated coatings deposited at p_CH4/p_t > 0.42, the friction coefficients and abrasive wear rates were shown to decrease with increasing a-C:H phase content and its more sp²-like bonding configuration. It can be concluded that the microstructural changes in terms of CrC _x crystallite coarsening and bonding configuration of the a-C:H matrix phase are responsible for the observed changes of the friction coefficients and wear rates.     

Aqueous Lubrication of SiC and Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Ceramics Aided by a Brush-like Copolymer Additive,Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lysine)-<Emphasis Type="Italic">graft</Emphasis>-poly(ethylene glycol)

We have examined the adsorption properties of poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG)—a brush-like polymer—on Si₃N₄ and SiC surfaces and determined its impact on the aqueous lubrication of Si₃N₄ and SiC at various speeds and applied loads. The addition of PLL-g-PEG in aqueous solution reduces the interfacial friction forces significantly for self-mated sliding contacts of these two ceramics, as compared to lubrication with water or buffer solution alone. For SiC, the improved lubricating performance by addition of PLL-g-PEG was apparent for all tested speeds (from 1.4 to 185 mm/s under 2 N load). For Si₃N₄, the effect was more apparent in the slow-speed regime (≤20 mm/s under 2 N load) than in the high-speed regime (>100 mm/s), where extremely low coefficients of friction (μ ≤ 0.006) are readily achieved by aqueous buffer solution alone. It was further observed that the optimal lubricating effect with Si₃N₄ is achieved when the tribopairs are first run-in in polymer-free aqueous buffer to render the sliding surfaces smooth, after which the PLL-g-PEG copolymer is added to the buffer solution.     

Dry and oil-lubricated sliding wear of Si<Subscript>3</Subscript>N<Subscript>4</Subscript> and Si<Subscript>3</Subscript>N<Subscript>4</Subscript>/BN fibrous monoliths

A high-temperature ball-on-flat tribometer was used to investigate dry and oil-lubricated friction and wear of sintered Si₃N₄ and Si₃N₄/hexagonal boron nitride (H-BN) fibrous monoliths. The friction coefficients of base Si₃N₄ flats sliding against Si₃N₄ balls were in the range of 0.6–0.8 for dry and 0.03–0.15 for lubricated sliding, and the average wear rates of Si₃N₄ were 10^–5 mm³ N^–1 m^–1 for dry sliding and 10^–10–10^–8 mm³ N ^–1m^–1 for lubricated sliding. The friction coefficients of Si₃N₄ balls against composite fibrous monoliths were 0.7 for dry sliding and 0.01–0.08 for lubricated sliding. The average specific wear rates of the pairs were of the same order as those measured for the conventional Si₃N₄ pairs. However, the fibrous monoliths, in combination with sprayed dry boron nitride, resulted in reduction in the lubricated friction coefficients of the test pairs and significant reduction in their wear rates. The most striking result of this study was that the coefficients of friction of the Si₃N₄/H-BN fibrous monolith test pair were 70–80 lower than those of either roughened or polished Si₃N₄ when tests were performed under oil-lubricated sliding conditions over long distances (up to 5000 m). The results indicated that Si₃N₄/H-BN fibrous monoliths have good wear resistance and can be used to reduce friction under lubricated sliding conditions.     

Effects of ZnO and MoS<Subscript>2</Subscript> Solid Lubricants on Mechanical and Tribological Properties of M50-Steel-Based Composites at High Temperatures: Experimental and Simulation Study

Prospective beneficial effects of mixtures of temperature-adaptive solid lubricants (ZnO–MoS₂) on mechanical and tribological properties of M50 alloy steel were investigated at temperatures from 25 to 800 °C. ZnO and MoS₂ were mixed with M50 (designated as M) to create composites MZ (M50 steel plus ZnO), MM (M50 steel plus MoS₂), and MZM (M50 steel plus both additives). Sliding friction and wear experiments were performed at different temperatures using a pin-on-disk at a sliding speed of 0.2 m s^?1 and a load of 12 N. Silicon nitride and M50 steel were used as the pin materials. In order to understand the friction and wear behavior of composites, analyses of their surfaces were done using XRD, EPMA, FESEM, EDS line/mapping, and XPS tests. A dynamic simulation model based on the finite element method was built to simulate the different stresses on the contact pairs. Results elucidated that MZM attained the least friction (0.17), compared to M (0.40), MZ (0.26), or MM (0.29) at 800 °C. The increase in surface roughness of MZM due to sliding was reduced by 37.3% compared to that of MZ (11.9%) or MM (22.7%). The good lubricating behaviors were referred to the synergetic effects of ZnO, MoS₂, and formed lubricating components on worn surfaces.     

Friction and wear properties of CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/SiC in water lubrication

Amorphous carbon nitride coatings (a-CN_x) were deposited on SiC disk by ion beam assisted deposition (IBAD). The tribological behavior of a-CN_x coating sliding against SiC ball in water was investigated and compared with that of SiC/SiC system at room temperature. The influences of testing conditions on friction coefficient and specific wear rate of both kinds of tribopairs were studied. The worn surfaces on disks were observed by scanning electron microscope (SEM). The results indicate that the running-in period of a-CN_x/SiC was shorter than that of SiC/SiC system in water. At a sliding velocity of 120 mm/s, the mean steady-state friction coefficients of SiC/SiC (0.096) was higher than that of a-CN_x/SiC (0.05), while at 160 mm/s, lower friction coefficient (0.01) was obtained for SiC/SiC in water. With an increment of normal load, the mean steady-state friction coefficients after running-in first decreased, reaching a minimum value, and then increased. For self-mated SiC, the specific wear rate of SiC ball was a little higher than that of SiC disk, while for a-CN_x/SiC, the specific wear rate of SiC ball were 10 times smaller than that of a-CN_x coating. Furthermore, the specific wear rate of SiC ball sliding against a-CN_x coating was reduced by a factor up to 100~1000 in comparison to that against SiC in water. The wear mechanism of SiC/SiC system in water is related to micro-fracture of ceramic and instability of tribochemical reaction layer. Conversely, wear mechanism for a-CN_x/SiC is related to formation and transfer of easy-shear friction layer.     

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 Property of Ni<Subscript>3</Subscript>Al Matrix Composites with Addition of BaMoO<Subscript>4</Subscript>

The Ni₃Al matrix composites with addition of 10, 15, and 20 wt% BaMoO₄ were fabricated by powder metallurgy technique, and the tribological behaviors were studied from room temperature to 800 °C. It was found that BaAl₂O₄ formed during the fabrication process. The Ni₃Al composites showed poor tribological property below 400 °C, with high friction coefficients (above 0.6) and wear rates (above 10⁻⁴ mm³/Nm). However, the composites exhibited excellent self-lubricating and anti-wear properties at higher temperatures, and the composite with addition of 15 wt% BaMoO₄ had the lowest wear rate (1.10 × 10⁻⁵ mm³/Nm) and friction coefficient (0.26). In addition, the results also indicated that BaAl₂O₄ for the Ni₃Al composites did not exhibit lubricating property from room temperature to 800 °C.     

Dry-sliding Tribological Properties of Nano-Eutectic Fe<Subscript>83</Subscript>B<Subscript>17</Subscript> Alloy

This paper reports the tribological performance of the nano-eutectic Fe₈₃B₁₇ alloy under dry sliding against Si₃N₄ ceramic ball in ambient environment with varying applied loads and sliding speeds. Worn surfaces of the nano-eutectic Fe₈₃B₁₇ alloy were examined with a scanning electron microscope (SEM) and an X-ray energy dispersive spectroscope (EDS). The wear debris of the samples were also analyzed by X-ray diffractometer (XRD). The wear rate of the nano-eutectic Fe₈₃B₁₇ alloy was of the magnitude of 10⁻⁴ mm³/m, which was lower than that of the coarse grained Fe₈₃B₁₇ alloy. The friction coefficient of the nano-eutectic Fe₈₃B₁₇ alloy was almost the same as that of the coarse grained Fe₈₃B₁₇ alloy. The Fe₂SiO₄ oxide layer was formed on the worn surface of the nano-eutectic Fe₈₃B₁₇ alloy. However, on the worn surface of the coarse grained Fe₈₃B₁₇ alloy was found only a little Fe₂SiO₄. These results demonstrated that the nanostructure improved the wear resistance of the Fe₈₃B₁₇ alloy, but did not significantly affect the friction coefficient. The wear mechanism of the nano-eutectic Fe₈₃B₁₇ alloy was delamination abrasion mainly.     

Tribological Performance of Fe<Subscript>67</Subscript>B<Subscript>33</Subscript> Alloy Prepared by a Self-Propagating High-Temperature Synthesis Technique

A bulk Fe₆₇B₃₃ alloy was prepared by a self-propagating high-temperature synthesis technique that is convenient, low in cost, and capable of being scaled up for tailoring the bulk materials. The Fe₆₇B₃₃ alloy is composed of dendrites with the t-Fe₂B phase and eutectic matrix with the α-Fe and t-Fe₂B phases. The content of the dendrite t-Fe₂B is above 80 vol.%. The compressive fractured strength and Vickers microhardness are 3400 MPa and 12.4 GPa, respectively. The tribological performance of the Fe₆₇B₃₃ alloy is investigated under dry sliding and water lubricant against Si₃N₄ ceramic ball. The wear rates of the Fe₆₇B₃₃ alloy are of the magnitude of 10⁻⁵ to 10⁻⁴ mm³/m under water lubricant. It is lower than that of the Fe₆₇B₃₃ alloy under dry sliding (10⁻⁴ mm³/m). But both the friction coefficients are almost identical. Oxide layers form in both environments via different tribochemical mechanisms, which led to significant differences in wear behavior.