The Formation of Tribofilms of MoS2 Nanotubes on Steel and DLC-Coated Surfaces

Solid-lubricant nanoparticles as additives in oil provide good tribological properties based on the physical lubrication mechanisms in the contact. For this reason, they are strong candidates for use in the lubrication of diamond-like carbon (DLC) coatings, which only poorly interact with the traditional, chemically based additives. In this study, we focused on how a tribofilm formed from MoS₂ nanotubes is related to the tribological properties of these nanotubes, and then, we analysed such a tribofilm on steel and DLC-coated surfaces using scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Auger electron spectroscopy. We demonstrated that when using oil containing MoS₂ nanoparticles, the formation of a tribofilm is a key factor in decreasing the friction for the steel and DLC-coated contacts. The major difference between the steel and the DLC contacts is the extent to which the MoS₂-based tribofilm covers the surface, which is 20 % in the case of the DLC/DLC contacts, but almost 40 % in the case of the steel/steel contacts. Moreover, the MoS₂-based tribofilm was found to be more oxidized on the DLC surface than on the steel surface. Nevertheless, we found that the chemical and functional properties of the MoS₂-based tribofilm are very similar, or even the same, for both the steel and DLC-coated surfaces. No direct evidence of any chemical reactions between the MoS₂ and the steel or DLC coating was observed.     

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.     

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.     

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.     

Tribochemical Formation of Sulphide Tribofilms from a Ti–C–S Coating Sliding Against Different Counter Surfaces

Tribochemically active Ti–C–S coatings are nanocomposite coatings containing a S-doped titanium carbide, from which S can be released in a tribological contact. This work studies tribochemical reactions between a Ti–C–S coating and various counter surface materials, and their effect on the tribological performance. Tribological tests were performed in a ball-on-disc set-up, using balls of five different materials as sliding partners for the coating: 100Cr6 steel, pure W, WC, 316-L steel and Al₂O₃. For W balls, a WS₂ tribofilm was formed, leading to low friction (down to µ = 0.06). Furthermore, increasing normal load on the W balls was found to lead to a strong decrease in µ and earlier formation of the low-friction WS₂ tribofilm. Similar WS₂ and MoS₂ tribofilms were, however, not formed from WC- and Mo-containing 316-L balls. The performance when using WC and Al₂O₃ balls was significantly worse than for the two steel balls. It is suggested that this is due to sulphide formation from Fe, analogous to formation of anti-seizure tribofilms from S-containing extreme pressure additives and steel surfaces. The tribochemical activity of Ti–C–S coatings, with the possibility of S release, is thus beneficial not only for pure W counter surfaces, but also for Fe-based sliding partners.     

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.     

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.     

Transient processes of MoS2 tribofilm formation under boundary lubrication

A tribochemistry study that involves the application of Raman spectroscopy surface analysis has been undertaken to understand the time‐dependent tribochemical reactions, for lubrication by Molybdenum dialkyl‐dithiocarbamate (MoDTC) occurring in boundary lubricated conditions. Under the conditions of rubbing and high temperature, time‐resolved Raman spectroscopy results show the intermediate steps that lead to the MoDTC additive to be tribochemically structured on the wear scar of the contacting surface. A MoS₂ tribofilm with a lattice layer structure is observed on the wear scar whenever the lowest friction was achieved. An apparent shift of the A_1g and E_2g Raman modes, indicating qualitative and quantitative information on the MoS₂ tribofilm formed, is observed to be related to low friction. Detailed analyses of Raman spectra obtained on wear scars at different test durations and temperatures indicate that both temperature and rubbing are needed for the formation of low friction MoS₂ tribofilm. Copyright © 2016 John Wiley & Sons, Ltd.     

Understanding the Tribochemical Mechanisms of IF-MoS<Subscript>2</Subscript> Nanoparticles Under Boundary Lubrication

Inorganic fullerene-(IF)-like nanoparticles made of metal dichalcogenides (IF-MoS₂, IF-WS₂) have been known to be effective as anti-wear and friction modifier additives under boundary lubrication. The lubrication mechanism of these nanoparticles has been widely investigated in the past and it is now admitted that their lubrication properties are attributed to a gradual exfoliation of the external sheets of the particles during the friction process leading to their transfer onto the asperities of the reciprocating surfaces. However, the chemical interaction between these molecular sheets and the rubbing surfaces has so far never been investigated in detail. In this study, the tribochemistry of the IF nanoparticles was carefully investigated. A series of friction test experiments on different rubbing surfaces (Steel, Alumina, Diamond-Like Carbon) were performed with IF-MoS₂ nanoparticles. High-resolution transmission electron microscopy, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the tribostressed areas on rubbing surfaces. A tribofilm composed of hexagonal 2H-MoS₂ nanosheets was only observed on the steel surface. This transfer film was found to be incorporated into an iron oxide layer. A tribochemical reaction between the 2H-MoS₂ nanolayers and the iron/iron oxide has been proposed as an explanation for the adhesion of this tribofilm. The tribochemical mechanism of the IF-MoS₂ nanoparticles is discussed in this article.     

Lubrication of carbon coatings with MoS2 single sheet formed by MoDTC and ZDDP lubricants

The fuel economy and reduction of harmful elements of lubricants are becoming important issues in the automotive industry. One approach to these requirements is the potential use of low‐friction coatings in engine components exposed to boundary lubrication conditions. Diamond‐like carbon (DLC) coatings, extensively studied as ultra‐low friction films to protect ductile metals surfaces for space applications, are expected to fit the bill. The main purpose of this work is to investigate the friction and wear properties of DLC coatings lubricated with molybdenum dithiocarbamate (MoDTC) and zinc dithiophosphate (ZDDP) under boundary lubrication conditions. The mechanisms by which MoDTC reduces the friction in the centirange were studied using ultra‐high vacuum (UHV) analytical tribometer. The UHV friction tests were performed on a tribofilm previously formed on selected DLC material with MoDTC and ZDDP containing oil. Ex‐situ characterizations show that the composition of this tribofilm is similar to that of a tribofilm obtained on steel surfaces in the same lubrication conditions with MoS₂ single sheets dispersed inside zinc phosphate zones. However, analyses by X‐ray photoelectron spectroscopy (XPS) indicate that MoDTC and ZDDP additives seem to be more active on steel surfaces than carbonaceous ones. After UHV friction with the tribofilm formed on selected DLC and steel pin counterpart, the wear scars of both sliding surfaces were characterized by in‐situ analytical tools such as Auger electron spectroscopy, scanning Auger microscopy and micro‐spot XPS. Low friction is associated with the transfer of a thin MoS₂ film to the steel pin counterpart. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of Layered MoS2 Nanoparticles on the Frictional Behavior and Microstructure of Lubricating Greases

Lithium stearate soap and layered MoS₂ nanoparticles encapsulated in lithium stearate soap are prepared in the laboratory, and their lubricating properties are compared with respect to the particle and particle concentration. The tribotracks after friction test was investigated with Raman Spectroscopy, scanning electron microscopy (SEM) and 3D optical profilometry to understand the action mechanism. The status of the soap particles on a tribotrack changes with time, contact pressure and sliding speed. At low pressure and speed, individual solid undeformed soap particle stand proud of the surface and the topography shows marginal difference with sliding time. In these conditions, no frictional difference between the performance of grease with and without the nanoparticles is observed. Increasing the contact pressure and temperature (low speed and high speed) has a dramatic effect as the soap particles melt and the liquid soap flows over the track releasing the hitherto encapsulated nanoparticles. Consequently, the soap smears the track like a liquid, and the nanoparticles now come directly into the interface and are sheared to generate a low-friction tribofilm. At high particle concentration, the sliding time required for melting of the soap and release of MoS₂ is reduced, and the tribofilm is more substantial and uniform consisting of smeared MoS₂ and carboxylate soap as observed by SEM and 3D optical profilometry. A change in the Raman Spectra is observed with particle concentration, and this is related to morphology and microstructure of the tribofilm generated.     

Adaptive Mo2N/MoS2/Ag Tribological Nanocomposite Coatings for Aerospace Applications

Reactively sputtered Mo₂N/MoS₂/Ag nanocomposite coatings were deposited from three individual Mo, MoS₂, and Ag targets in a nitrogen environment onto Si (111), 440C grade stainless steel, and inconel 600 substrates. The power to the Mo target was kept constant, while power to the MoS₂ and Ag targets was varied to obtain different coating compositions. The coatings consisted of Mo₂N, with silver and/or sulfur additions of up to approximately 24 at%. Coating chemistry and crystal structure were evaluated using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), which showed the presence of tetragonal Mo₂N and cubic Ag phases. The MoS₂ phase was detected from XPS analysis and was likely present as an amorphous inclusion based on the absence of characteristic XRD peaks. The tribological properties of the coatings were investigated in dry sliding at room temperature against Si₃N₄, 440C stainless steel, and Al₂O₃. Tribological testing was also conducted at 350 and 600 °C against Si₃N₄. The coatings and respective wear tracks were examined using scanning electron microscopy (SEM), optical microscopy, profilometry, energy dispersive X-ray spectroscopy (EDX), and micro-Raman spectroscopy. During room temperature tests, the coefficients of friction (CoF) were relatively high (0.5–1.0) for all coating compositions, and particularly high against Si₃N₄ counterfaces. During high-temperature tests, the CoF of single-phase Mo₂N coatings remained high, but much lower CoFs were observed for composite coatings with both Ag and S additions. CoF values were maintained as low as 0.1 over 10,000 cycles for samples with Ag content in excess of 16 at% and with sulfur content in the 5–14 at% range. The chemistry and phase analysis of coating contact surfaces showed temperature-adaptive behavior with the formation of metallic silver at 350 °C and silver molybdate compounds at 600 °C tests. These adaptive Mo₂N/MoS₂/Ag coatings exhibited wear rates that were two orders of magnitude lower compared to Mo₂N and Mo₂N/Ag coatings, hence providing a high potential for lubrication and wear prevention of high-temperature sliding contacts.     

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.     

In Situ Raman Observations of the Formation of MoDTC-Derived Tribofilms at Steel/Steel Contact Under Boundary Lubrication

ABSTRACT

In this study, the time-dependent formation process of molybdenum dithiocarbamate (MoDTC)-derived tribofilms at steel/steel contact under boundary lubrication was investigated by using an in situ Raman tribometer. Especially, we focused on the effects of zinc dialkyldithiophosphate (ZDDP) concentration in MoDTC solution on MoDTC tribofilm formation process. A laboratory-built in situ Raman tribometer was used to evaluate friction and the formation process of MoDTC-derived tribofilms. All our results clearly suggest that there is an optimum ZDDP concentration in MoDTC solution for promoting the formation of MoS₂ tribofilms on the sliding surfaces, and there is also a threshold value for the formation rate of MoS₂ on the sliding surface for achieving low friction under lubrication with MoDTC-containing lubricants.     

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.     

Microstructure and lubrication mechanism of multilayered MoS2/Sb2O3 thin films

Multilayered MoS₂/Sb₂O₃ thin films were prepared by pulsed laser deposition on steel substrates. A rotary multi-target holder was used to switch the laser targets for alternative growth of MoS₂ and Sb₂O₃ layers providing nanometers thickness. The tribological properties of the films were measured in dry and wet environments and the wear scars were observed using a scanning electron microscope. The multilayer films showed a much longer wear life than pure MoS₂ films in wet air tribotests. Focused ion beam and transmission electron microscopies were used to investigate the cross-sectional microstructures of wear scars. Lubricious MoS₂/Sb₂O₃ tribofilms were built up on wear scar surfaces, and produced low friction. Micro-cracks occurred along the interface between the tribofilm and the neighboring/topmost Sb₂O₃ underlayer, where the Sb₂O₃ layer effectively inhibited the crack propagation perpendicular to the interface. The orientation of MoS₂ crystals in as-deposited films was mostly random and friction-induced stress oriented the MoS₂ basal planes parallel to the surface. The reorientation was confined to the topmost MoS₂ layer and was not observed below the first intact Sb₂O₃ layer.     

Relationship of Endurance to Microstructure of IBAD MoS2 Coatings

The endurance of ion-beam-assist-deposited (IBAD) MoS₂ is correlated with coating structure and orientation. Structure and orientation are determined by X-ray diffraction, while endurance is measured with a ball-on-disk tribometer operating in dry air. The IBAD MoS₂ coatings contain both crystalline and non-crystalline components. Only two orientations of the crystalline component are observed: the (001) planes parallel (basal orientation) and perpendicular (edge orientation) to the surface. Endurance of the coating is not related to coating thickness or substrate chemistry, but is related to the relative amount of the two MoS₂ crystal orientations. Coating endurance decreases with increasing edge (100) intensity. Furthermore, MoS₂ coatings with poor crystallinity exhibit good endurance. These results are discussed in terms of a possible oxidative wear mechanism and stress-induced basal re-orientation of the non-crystalline IBAD MoS₂.     

High Wear Resistance of Magnetron Sputtered Cr<Subscript>80</Subscript>Si<Subscript>20</Subscript>N Nanocomposite Coatings: Almost Independent of Hardness

Hardness has been popularly considered as an essential factor defining the wear resistance of hard coatings. Here, we report magnetron sputtered Cr₈₀Si₂₀N nanocomposite coatings, of widely varied packing densities, that exhibited identical specific wear rates, while the hardness changed over a wide range (from ~12 to ~36 GPa). All the Cr₈₀Si₂₀N coatings were free of extended and uninterrupted columnar boundaries, and retained low specific wear rates in the ball-on-plate sliding tests against Al₂O₃ counterpart with a normal load of 5 N (less than 3.0?×?10^?16 m³/N m under ambient condition and less than 2.0?×?10^?15 m³/N m under 3.5 wt% NaCl solution, respectively). Post examination reveals extensive interruption or termination of cracks in the wear tracks of the under-dense coatings, indicative of extrinsic toughening mechanisms by effective relief of local contact stress. Our results suggest that a critical role of toughening rather than hardening, played in enhancing the wear resistance of hard coatings, and thus would pave a way to develop highly wear-resistant coatings with a low hardness.     

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.