The Effects of Environmental Water and Oxygen on the Temperature-Dependent Friction of Sputtered Molybdenum Disulfide

Molybdenum disulfide (MoS₂) is well known for exceptional friction and wear properties in inert and high vacuum environments. However, these tribological properties degrade in humid and high temperature environments for reasons that are not fully understood. A prevailing hypothesis suggests that moisture and thermal energy facilitate oxidation, which increases the shear strength of the sliding interface. The purpose of this study is to elucidate the contributions of water, oxygen, and temperature to the tribological degradation of MoS₂. Generally speaking, we found a minimum friction coefficient that occurred at a temperature we defined as the transition temperature. This transition temperature ranged from 100 to 250 °C and was a strong function of the MoS₂ preparation and thermal sliding history. Below the transition temperature, friction increased with increased water, but was insensitive to oxygen. Above the transition, friction increased with increased oxygen, but decreased to a limited extent with increased water. These results are generally consistent with prior results, but clarify some inconsistencies in the literature discussions. Contrary to the prevailing hypothesis, the results suggest that water does not promote oxidation near room temperature, but directly interferes with lamellar shear through physical bonding. Increased temperatures drive off water and thereby reduce friction up to the transition temperature. The results suggest that oxidation causes increased friction with increased temperature above the transition temperature. The data also suggest that water helps mitigate high temperature oxidation by displacing the environmental oxygen or by preferentially adsorbing to the surface.     

Comparison of Macro and Microtribological Property of Molybdenum Disulfide Film Exposed to LEO Space Environment

Macro- and microtribological properties of the MoS₂ film exposed to atomic oxygen, ultraviolet rays and radiation both in low earth orbit (LEO) and in ground-based facility were evaluated relevance to micro/nano satellites. MoS₂ samples are exposed to LEO space environment by the space environment exposure device experiment on international space station. Laser-detonation atomic oxygen beam source was used for atomic oxygen simulation on the ground. X-ray photoelectron spectroscopy and energy dispersive spectroscopy measurements suggested that electron beam and ultraviolet exposure did not affect chemical structure of MoS₂ surfaces. However, atomic oxygen-exposed and flight samples showed surface oxidation. It was found that the macroscopic friction coefficient of the flight sample was similar to that of the control sample. In contrast, remarkable increase in friction coefficient in microscopic properties was observed.     

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.     

The Effect of Humidity on Low-Load Frictional Properties of a Bonded Solid Film Lubricant

Low-load slow-speed sliding friction tests were conducted on a MoS₂/graphite (90/10) bonded solid film lubricant in controlled-humidity environments. The average steady-state coefficient of friction increased from 0.23 to 0.28 as relative humidity (RH) was raised from 10 percent to 50 percent, and it increased to 0.6 when RH reached 90 percent.

At RH ≥80 percent, friction response was strongly influenced by chemically reactive metals used for slider and lubricant substrate. Thus, friction with carbon steel sliders was significantly lower than with stainless steel sliders, although corrosion of the former caused rapid destruction of the lubricant film. Also, continued sliding by stainless steel on lubricant applied to phosphor-bronze eventually resulted in a significant friction decrease and simultaneous formation of a dark red-brown film in the wear track. The proposed explanation for these effects is based on oxidation of MoS₂ at the sliding interface and reaction of the oxidation products with slider and substrate metals.     

Environmental Effects on the Composition of Surface Films Produced by an Organo-Molybdenum Compound©

The influence, of environments on the properties of the surface films formed, with molybdenum dithiocarbamate (MoDTC) was examined under a reciprocating sliding condition. MoS₂ was formed on the rubbing surfaces in air and oxygen, and molybdenum compounds with an oxidation state lower than MoS₂ were produced in nitrogen and argon. The surface film composed of MoS₂ was effective in reducing the friction and wear, while the molybdenum compound formed in nitrogen or argon had no ability to prevent direct contact between the rubbing surfaces and to reduce the friction. It was a necessary condition for forming the surface film composed of MoS₂ that the environment to be rubbed contained oxygen at a concentration above a certain level.     

Effect of strain on atomic-scale friction in layered MoS2

The atomic-scale friction in MoS₂ is investigated employing the density functional theory calculation including the dispersion correction (DFT-D). Energy corrugations and lateral frictional forces of the lamellar MoS₂ are derived, suggesting that the in-plane compressive MoS₂ exhibits lower friction than the tensile system. The reduced friction is attributed to a stronger coulombic repulsive interaction enabled by the transferred charge to the sliding interface. In-depth understanding of the relationship between friction and interfacial interaction shows that friction can be tuned in layered MoS₂ by applying an in-plane strain to the sliding interface.     

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.     

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 Importance of Variable Speeds under Extreme Pressure Loading in Molybdenum Disulfide Greases Using Four-Ball Wear Tests

There is recent concern regarding grease behavior in extreme pressure applications. The research described here is aimed at providing good friction and wear performance while optimizing rotational speeds under extreme loading conditions. A design of experiment (DOE) was used to analyze molybdenum disulfide (MoS₂) greases and their importance in reducing wear under extreme loading and various speeds conditions (schedule 1 and schedule 2 speeds). The lamellar structure of MoS₂ provides very good weld protection by forming a layer that can be easily sheared under the applications of extreme pressures. An extreme load of 785 N was used in conjunction with different schedules of various rotational speeds to examine lithium-based grease with and without MoS₂ for an equal number of revolutions. A four-ball wear tester was utilized to run a large number of experiments randomly selected by the DOE software. The grease was heated to 75°C and the wear scar diameters were collected at the end of each test.

The results indicated that wear was largely dependent on the speed condition under extreme pressure loading, and thus a lower MoS₂ concentration is needed to improve the wear resistance of lithium-based greases. The response surface diagram showed that the developed molybdenum disulfide greases exhibited both extreme pressure as well as good wear properties under various rotational speeds when compared to steady-state speed. It is believed that MoS₂ greases under schedule 1 speeds perform better and provide an antiwear film that can resist extreme pressure loadings.     

A comparison of oxidation and oxygen substitution in MoS2 solid film lubricants

Significant advancements in the production of low friction, long wear life, sputter-deposited MoS₂ lubricant coatings have been made in the last decade. The introduction of multi-layered coatings, the establishment of careful controls on doping during DC and magnetron sputter deposition, and the implementation of ion assisted deposition have resulted in lubricants with substantially longer wear lives (up to a factor of ten greater than in the early 1980s) and lower sliding friction coefficients. A major research effort, designed to improve the performance of solid lubricants, involved a number of laboratories during this time period, resulting in these major breakthroughs. However, even with this concentrated effort, the typical investigation involved making an educated guess, based on previous experience, of the deposition conditions, target compositions, or post treatments that might be expected to provide improved performance of resulting coatings. One notable discovery during this time period was that typical MoS₂ films contain large quantities (up to 20 atom %) of oxygen substituted for sulfur in individual crystal lattices. In this paper we will compare the effects of this oxygen substitution with the effects of oxidation which involves a change in the oxidation number of the central molybdenum atoms within the crystals. A discussion of the relationship(s) between chemistry and coating structure and tribological performance will be presented with emphasis on defect chemistry and multiple phase interactions. Speculations on the role of coating chemistry in determining coating performance in applications such as in ball bearings will be presented.     

Super-low friction of MoS2 coatings in various environments

The ultra-low friction coefficient (typically in the 10⁻² range) of MoS₂-based coatings is generally associated with the friction-induced orientation of ‘easy-shear’ planes of the lamellar structure parallel to the sliding direction, particularly in the absence of environmental reactive gases and with moderate normal loads. We used and AES/XPS ultra-high vacuum tribometer coupled to a preparation chamber, thus allowing the deposition of oxygen-free MoS₂ PVD coatings and the performance of friction tests in various controlled atmospheres. Friction of oxygen-free stoichiometric MoS₂ coatings deposited on AISI 52100 steel was studied in ultra-high vacuum (UHV: 5 × 10⁻⁸ Pa), high vacuum (HV: 10⁻³ Pa), dry nitrogen (10⁵ Pa) and ambient air (10⁵ Pa). ‘Super-low’ friction coefficients below 0.004 were recorded in UHV and dry nitrogen, corresponding to a calculated interfacial shear strength in the range of 1 MPa, about ten times lower than for standard coatings. Low friction coefficients of about 0.013–0.015 were recorded in HV, with interfacial shear strength in the range of 5 MPa. Friction in ambient air leads to higher friction coefficients in the range of 0.2. Surface analysis performed inside the wear scars by Auger electron spectroscopy shows no trace of contaminant, except after friction in ambient air where oxygen and carbon contaminants are observed. In the light of already published results, the ‘super-low’ friction behaviour (10⁻³ range) can be attributed to superlubricity, obtained for a particular combination of cystallographic orientation and the absence of contaminants, leading to a considerable decrease in the interfacial shear strength.     

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.     

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.     

Tribological properties of molybdenum disulphide nanoparticles in soybean oil

Abstract

The tribological properties of soybean oil (SO) with different molybdenum disulfide (MoS₂) additives (hollow nanosphere, nanoplatelet and microplatelet) were investigated. MoS₂ hollow nanospheres remarkably improved the tribological properties of SO. SO with MoS₂ hollow nanospheres decreased abrasive plowing and changed the main wear pattern on the steel friction surfaces into chemical corrosion. The MoS₂ hollow nanospheres easily entered the contact region than the other MoS₂ particles to lubricate the friction pair because of its good dispersibility in SO. The tribochemical reactions among MoS₂ hollow nanospheres, SO and friction material produced a lubricating film composed of MoO₃, Fe₂O₃, carbon containing compounds. Thus, the MoS₂ hollow nanospheres have potential lubricating applications with SO. By contrast, MoS₂ nanoplatelet and microplatelets had lesser effects on the lubricating effect of SO. The MoS₂ nanoplatelets, even with its smaller size and more active chemical properties, had more difficulty in entering into the contact region because of its low dispersibility in the base oil.     

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.     

Dry Sliding Friction and Wear Characteristics of Cu-Sn Alloy Containing Molybdenum Disulfide

The wear and sliding friction response of a hybrid copper metal matrix composite reinforced with 10 wt% of tin (Sn) and soft solid lubricant (1, 5, and 7 wt% of MoS₂) fabricated by a powder metallurgy route was investigated. The influence of the percentages of reinforcement, load, sliding speed, and sliding distance on both the wear and friction coefficient were studied. The wear test with an experimental plan of six loads (5–30 N) and five sliding speeds (0.5–2.5 m/s) was conducted on a pin-on-disc machine to record loss in mass due to wear for two total sliding distances of 1,000 and 2,000 m. The results showed that the specific wear rate of the composites increased at room temperature with sliding distance and decreased with load. The wear resistance of the hybrid composite containing 7 wt% MoS₂ was superior to that of the other composites. It was also observed that the specific wear rates of the composites decreased with the addition of MoS₂. The 7 wt% MoS₂ composites exhibited a very low coefficient of friction of 0.35. The hardness of the composite increased as the weight percentage of MoS₂ increased. The wear and friction coefficient were mainly influenced by both the percentage of reinforcement and the load applied. Wear morphology was also studied using scanning electron microscopy and energy-dispersive X-ray analysis.     

A study of the influence of lanthanum fluoride on the tribological properties of bonded solid film lubricants and its mechanism of function

The influence of lanthanum fluoride (LaF₃) on the characteristics of phenolepoxy-bonded MoS₂ dry films was investigated. The functional mechanism was specifically studied using several analytical means. The results showed that the wear life of dry films containing a certain amount of LaF₃ was considerably increased over that of the films without LaF₃. However, the effect of LaF₃ on the friction coefficient of the dry films was shown to be negligible. It was found that the addition of LaF₃ is effective in reducing the oxidation tendency of MoS₂ in the films during the friction process. The reason for this is investigated by the authors.     

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.     

Friction and Wear Properties of TiAl-Ti3SiC2-MoS2 Composites Prepared by Spark Plasma Sintering

TiAl matrix self-lubricating composites (TMC) with various weight percentages of Ti₃SiC₂ and MoS₂ lubricants were prepared by spark plasma sintering (SPS). The dry sliding tribological behaviors of TMC against an Si₃N₄ ceramic ball at room temperature were investigated through the determination of friction coefficients and wear rates and the analysis of the morphologies and compositions of wear debris, worn surfaces of TMC, and the Si₃N₄ ceramic ball. The results indicated that TMC with 10 wt% (Ti₃SiC₂-MoS₂) lubricants had good tribological properties due to the unique stratification subsurface microstructure of the worn surface. The friction coefficient was about 0.57, and the wear rate was 4.22 × 10^?4 mm³ (Nm)^?1. The main wear mechanisms of TMC with 10 wt% (Ti₃SiC₂-MoS₂) lubricants were abrasive wear, oxidation wear, and delamination of the friction layer. However, the main wear mechanisms of TMC without Ti₃SiC₂ and MoS₂ lubricants were abrasive wear and oxidation wear. The continuous friction layer was not formed on the worn surfaces. The self-lubricating friction layer on the frictional surface, different phase compositions and hardness, as well as density of TMC contributed to the change in the friction coefficient and wear rate.