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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Low-Friction MoS x Coatings Resistant to Wear in Ambient Air of Low and High Relative Humidity

The investigation of the tribological performance of MoS₂-based coatings in air of high humidity is critical for the future use of such low-friction and high-wear-resistant coatings in ambient air. Sulfur-deficient MoS _x coatings with a basal plane (x = 1.3) and a random (x = 1.8) crystallographic orientation were produced by planar magnetron sputtering. The coefficient of friction and the wear loss of MoS_x coatings in comparison with TiN and amorphous TiB₂ coatings were investigated in bi-directional sliding fretting tests performed in ambient air of different relative humidity. The wear rate expressed as a volumetric loss per unit of dissipated energy was determined. From these results, the best friction and wear performance was achieved with basal-plane-oriented MoS _x coatings tested at a relative humidity in the range of 10-50%. A coefficent of friction of 0.06-0.08 and a wear rate of 4 × 10³ m³J^-1, at a normal load of 1 N and a fretting frequency of 10 Hz, were recorded for that type of MoS _x coatings.     

Study on the tribological properties of surfactant-modified MoS2 micrometer spheres as an additive in liquid paraffin

Tribological properties of MoS₂ micrometer spheres modified by self-prepared surfactant as an additive in liquid paraffin (LP) are studied and compared with those of the commercial colloidal MoS₂ on a four-ball tester and an Optimol SRV oscillating friction and wear tester. The worn surfaces are examined with SEM and XPS, respectively. Results show that MoS₂ micrometer sphere is a much better extreme-pressure additive and anti-wear and friction-reducing additive in LP than the commercial colloidal MoS₂. The boundary lubrication mechanism can be deduced as an effective chemical adsorption protective film formed by the long chain alkyl and active elements (S and N) in the prepared surfactant and tribochemical reaction film composed of the tribochemical reaction products of the additive. Moreover, sliding and rolling frictions exist simultaneously in the MoS₂ micrometer spheres /LP lubricating system, which also do more contributions to the good tribological properties.     

Effect of Humidity on Lubricated Carbon Overcoats

An apparatus has been designed and built to measure the adsorption of contaminants on the surfaces of lubricated carbon overcoats such as those used on magnetic data storage media. The device is based on a quartz crystal microbalance housed in a high vacuum chamber and can be used to make rapid measurements of both the amounts and the rates of contaminant adsorption from the gas phase during exposure. Initial measurements of the adsorption of water during exposure to water vapor indicate that at room temperature and moderate humidity levels (50% RH) the amount of water on a surface is of the order of one adsorbed monolayer. Adsorption and desorption is remarkably rapid indicating that equilibrium with ambient humidity is reached on timescales of minutes. Finally, the comparison of H₂O and D₂O adsorption indicates that the adsorbed water either forms a hydrogen bonded network on the surface or is hydrogen bonded to some species exposed at the surface of the carbon overcoat.     

Development and research of a laser photo-acoustic SF<Subscript>6</Subscript> gas analyzer

An analysis of various optical schemes for the development of a laser SF₆ gas analyzer based on a CO₂ laser operating in free-running mode and a resonant photo-acoustic detector (PAD) is presented. The use of a sealed gas-filled cell to normalize PAD signals on the absorbed power in the cell is suggested. Compensation for the influence of the tuning of the CO₂ laser wavelength near 10.6 μm on measured SF₆ concentration is possible. The results of experimental studies of a laser photo-acoustic SF₆ gas analyzer at various concentrations, including in the air flow, are presented. It is shown experimentally that the relative measurement error of the SF₆ concentration due to the instability of the laser radiation wavelength does not exceed 5% in the range from ~80 ppb to 40 ppm. The limit of the sensitivity of the developed gas analyzer was ~1 ppb SF₆.     

The Role of Cerium in the Resistance of an MoS2-Containing Composite Brush Plating Layer to Humid Atmosphere

MoS₂ is an excellent solid lubricant widely used for reducing friction. However, moisture is very harmful to its solid lubrication property because MoS₂ is easily oxidized to form Mo⁶⁺ and S⁶⁺ in a humid atmosphere. In order to improve its oxidation resistance, a study on the role of a rare earth element Ce in the resistance of a Ni-Cu-P/Mo₂ brush plating layer to the humid atmosphere was carried out. It was found that cerium can effectively stabilize the solid lubrication property of MoS₂ due to its preferential adsorption on the surface of MoS₂ particles, the adsorbed layer serving as a barrier to oxidation. This study shows that the rare earth element Ce can be deposited from a water plating solution.     

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.     

Surface and Subsurface Contributions of Oxidation and Moisture to Room Temperature Friction of Molybdenum Disulfide

Molybdenum disulfide (MoS₂), a lamellar solid lubricant, is used extensively in space applications due to its exceptional performance in vacuum and inert environments. The friction and wear of MoS₂, however, increase in the presence of atmospheric contaminants, such as water. Despite numerous studies of the moisture-sensitive friction response of MoS₂ over the decades, important fundamental questions remain unanswered. Two leading hypotheses suggest that water affects friction by causing the MoS₂ to oxidize or by physically bonding to edge sites, and thereby disrupting easy lamellar shear. This paper presents a parametric study to (1) isolate the effects of water and oxygen on ambient MoS₂ friction, (2) identify the effect of water and oxygen on MoS₂ oxidation, and (3) distinguish between the effects of water diffusion and surface oxidation on the frictional response of MoS₂ coatings. The experimental findings were used to develop a qualitative model for the effects of environment on MoS₂ friction; the model is used to explain transients, hysteretic effects, oxidation effects, and effects of physically bound water.     

Investigation of Annealing Temperature on Structural and Morphological Properties of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanoparticles for Humidity Sensor Application

Cr₂O₃ nanoparticles have been prepared for precipitation technique at reaction temperature 50 °C. The prepared samples were annealed different temperatures at 500,700 and 1000 °C. Synthesized powders were characterized as X-ray diffraction, optical, transmission electron microscope, SEM with EDAX, humidity sensor, FTIR. The annealing temperature has been found to be playing a crucial role in the controlling particle size. XRD study shows the rhombohedral crystal structure of highly preferential orientation along (1 0 4) direction. FTIR reveals that the presence Cr–O bonds in the structure. The TEM images show that the size of NPs of Cr₂O₃ varied from 26 to 60 nm with average crystalline size 43 nm. UV–visible spectrum shows the absorption band of Cr₂O₃ nanoparticles at 400 nm. The humidity sensor of the Cr₂O₃ nanoparticles was studied by two temperature method. 1000 °C annealed Cr₂O₃ nanoparticles show better sensing properties and exhibits good linearity in response than 500 °C. SEM images show the clusters and agglomeration of nanoparticles. EDAX spectrum confirms the presence of Cr₂O₃ nanoparticles. Each samples have been characterized as sensing materials to determine relative humidity in the range of 20–90%. The humidity sensing property increased with increasing of annealing temperature and the resistance was decreased.     

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.     

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.