Tribochemistry of ZDDP and MoDDP chemisorbed films

By means of a UHV analytical AES/XPS pin-on-flat tribotester, we have investigated tribochemical change as well as transfer mechanisms in static reaction films on steel from ZDDP (anti-wear) and MoDDP (friction modifier) lubricant additives. The results show that solid ZDDP reaction films are able to strongly reduce friction to a value of 0.1–0.3 (in the absence of a film, steel-on-steel gives a friction coefficient value of up to 2). MoDDP reaction films produce ultra-low friction (below 0.05) after an induction period. In situ AES analysis and energy-filtered XPM gave definitive evidence of frictioninduced chemical changes and selective material transfer from the flat to the pin. In the case of MoDDP, the thiophosphate film is decomposed and a MoS₂ residual film is found in the wear scar on the pin.A lecture based on this paper was presented at the Satellite Forum on Tribochemistry, International Tribology Conference, Yokohama 1995, organized by the Tribochemistry Research Committee, Japanese Society of Tribologists.     

Tribochemical interactions between Zndtp,Modtc and calcium borate

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and overbased detergent calcium borate (OCB) lubricant additives have been investigated. Friction tests were performed in mild wear conditions under boundary lubrication, in order to enhance tribochemical surface effects. The nature of tribofilms formed was studied by coupling high‐resolution TEM on wear fragments and inside‐wear‐scar, micro‐spot XPS in the same location of the wear track (so‐called dual analysis). The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS₂ single sheets and the digestion of MoO₃ in the zinc polyphosphate glass formed. The final result of the tribochemical reaction is a two‐phase tribofilm composed of (i) non‐oriented MoS₂ sheets (friction modifier) embedded in a carbon‐rich phase and (ii) a mixed Zn/Mo polyphosphate glass (antiwear). The Modtc/OCB mixture has a similar antiwear mechanism except that the oxide is not completely eliminated, due to the softer action of borate anion compared with phosphate one. Compared to the data obtained with binary combinations (Modtc/Zndtp, Modtc/OCB and Zndtp/OCB), we show here that the ternary system Modtc/Zndtp/OCB provides both a low wear rate and an ultralow friction value, while adding detergent and anti‐corrosive properties to the formulation. Our analytical data indicate that the synergistic effect can be attributed to an outstanding nanostructure of the tribofilm formed. It is composed of a single‐phase material containing perfectly oriented MoS₂ single sheets embedded in a calcium and zinc borophosphate glass. The ternary system produces a smart material in the interface, because both functions (antiwear and friction reduction) are correlated. Compared to phosphate alone, the mechanism by which MoS₂ sheets have been oriented in the borophosphate could be related to aligned molecules of the glassy polymer in the direction of sliding. This revised version was published online in July 2006 with corrections to the Cover Date.     

Further investigation on the tribological behavior of Al2O3–20Ag20CaF2 composite at 650°C

The friction and wear behaviors of the self‐lubricating Al₂O₃–20Ag20CaF₂ disk against an Al₂O₃ pin pair have been investigated over a broad load range from 1 to 30 N and sliding velocities from 0.084 to 1 m/s at 650^°C. Four typical wear modes have been identified and the wear mode map was constructed to illustrate the influence of load and speed on the friction coefficient and wear rate. The results showed the effective self‐lubricating region (II) (continuous lubricating film) is almost independent of sliding speed, and mainly dependent on the load. It is suggested that the plastic deformation and plastic flow during sliding play an important role in the formation of the self‐lubricating film on the sliding surface. Furthermore, the worn surface in the region (II) (continuous lubricating film) was found to be much softer than the original surface and the distribution of Vickers hardness became more uniform due to the presence of the lubricating film on the worn surface. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synergistic effects in binary systems of lubricant additives: a chemical hardness approach

Tribochemical interactions between antiwear zinc dithiophosphate (Zndtp), friction modifier molybdenum dithiocarbamate (Modtc) and detergent overbased calcium borate (CB) lubricant additives have been investigated by coupling analytical TEM and micro‐spot XPS in the tribotester Optimol of SRV GmbH (mild wear conditions in boundary lubrication). Synergistic effects have been observed on both friction and wear data, especially in the Modtc/Zndtp combination. Results have been interpreted on the basis of a chemical hardness concept: the hard and soft acids and bases (HSAB) principle, stabilisation of hard–hard pairs and the maximum hardness principle. The performance of the Modtc/Zndtp mixture is mainly due to the generation of MoS₂ single sheets and the digestion of MoO₃, which is also formed, by the zinc polyphosphate glass. The final result of the tribochemical reaction is a tribofilm composed of MoS₂ sheets embedded in a mixed Mo/Zn polyphosphate glass. The CB/Modtc mixture has a similar mechanism except that the oxide is not completely eliminated, due to the softer borate anion compared with the phosphate one. This revised version was published online in July 2006 with corrections to the Cover Date.     

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

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

Extremely low coefficient of friction of diamond sliding against Ag thin films on Si(1 1 1) surface under ultrahigh vacuum condition

The tribological properties of a diamond (1 1 1) pin slid on subnanometer thick Ag films, which were deposited on a cleaned Si(1 1 1) substrate, were studied using a pin-on-plate tribometer. The preparation of Ag ultrathin films and frictional experiments were performed in an ultrahigh vacuum (UHV) chamber at a pressure of 10⁻⁸ Pa. The frictional experiments were carried out at a sliding speed of 0.1 mm/s and at a normal load of 250 mN. An extremely low coefficient of friction, less than 0.01, was obtained when the pin was slid on Ag films, whose thicknesses were 1 and 2.6 monolayer (ML) under reciprocal motion. The minimum coefficient of friction was less than 0.004 for Ag 1 ML film. After the extremely low coefficient of friction was obtained, Ag remained on the worn track without any transfer to the diamond pin, as confirmed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS).The mechanisms of extremely low coefficients of friction are discussed in terms of the chemical bonding force between atoms of the topmost layers, and Ag coverage on the Si surface.     

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.     

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

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

Tribological and nanoscale research on model friction couples intended for hip joint prostheses

Abstract

The paper presents the results of tribological and nanoscale research on model friction couples intended for hip joint prostheses. The tribological tests were performed by means of reciprocating pin on plate testing machine. The investigated friction pairs contained plates rubbing against polymer pins. The test plates were made from seven kinds of ceramics containing different concentrations of ZrO₂ and Al₂O₃, and two kinds of Co–Cr alloy. The test pins were made from UHMWPE. Tribological tests were performed in conditions of Ringer solution circulation. On the basis of friction force measurements, for each investigated friction couple, the average coefficient of friction was calculated. On the basis of total wear measurements, for each investigated couple, the wear intensity was calculated. Before and after every test, the plates and pins were analysed by means of atomic force microscopy. The difference in plate surface roughness was determined by the results of the atomic force microscopy analyses.

It was stated, that in the case of investigated friction joints, working under reciprocating motion, the wear and friction coefficient correlates with the surface roughness of plate specimens. For the plates with higher surface roughness, the lower friction coefficient and also lower UHMWPE pin wear intensity were observed. The friction coefficient and wear intensity were increasing with decreasing surface roughness. The correlation is confirmed by the differences in material transfer process. Considering investigated friction couples, the pin polymer material is smeared on the ceramic plates with the highest surface roughness creating a thin polymer film. In the case of ceramic surfaces with the lowest surface roughness, the strong adhesive bounds are created and some large particles of polymer are transferred to ceramic surface.     

Environmental effects on the friction of hydrogenated DLC films

We have investigated environmental effects on hydrogenated diamond-like carbon (H-DLC) films under various pressures of H₂O, O₂, and N₂ by ultrahigh vacuum (UHV) tribometry. The H-DLC film exhibits an ultralow coefficient of friction (μ = 0.004 in UHV). The μ value increases with increasing pressure of H₂O and O₂. Specifically, μ increases up to 0.07 under 10 Torr of H₂O, and up to 0.03 under 150 Torr of O₂; these are typical H₂O and O₂ contents respectively in ambient air. Our results are consistent with similar environmental effects previously reported. But, we have also discovered that these friction changes are reversible, returning to the ultralow value when UHV is restored. The reversibility of the friction behavior in both environments, coupled with the lack of evidence of tribochemical changes by Auger electron spectroscopy, suggest that the observed friction changes are due to the weakly adsorbed gas molecules that influence the friction property by physically separating the H-DLC interface. Speed-dependent tribometry also supports this argument. In addition, two DLC films with different hydrogen contents and with widely different friction coefficients in UHV are shown to exhibit identical μ values under humid environments, further demonstrating that the frictional properties of these DLC films are essentially determined by the surface layer of adsorbed gas molecules.     

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.     

Microfriction and macrofriction of metal containing amorphous hydrocarbon hard coatings determined by AFM and pin‐on‐disk tests

Metal containing amorphous hydrocarbon films (Me‐C:H) have excellent tribological properties and an adjustable electrical conductivity. Friction force microscopy investigations on gold‐ and tungsten‐C:H films show a non‐linear dependence of friction on the load in the nanonewton‐range which can be explained by Hertz model of elastic contact. The effective friction coefficient and the interfacial shear stress strongly depend on the type of metal and the metal concentration inside the film. Microfriction and macrofriction (pin‐on‐disk) show a high qualitative correspondence. This revised version was published online in June 2006 with corrections to the Cover Date.     

Tribological Performance of UHMWPE and PFPE Coated Films on Aluminium Surface

A thin layer of Ultra High Molecular Weight Polyethylene (UHMWPE) or UHMWPE + PFPE is coated onto cylindrical aluminium (Al) pin (4.6 mm diametre) surface with the aim of providing wear resistant coating on this soft and tribologically poor metal. The coefficient of friction and wear life of the coated samples are investigated on a pin-on-disk tribometre under different normal loads (394–622 g) and two sliding speeds (0.1 and 0.31 m/s) against uncoated Al disk as the counterface. Both coatings provide coefficient of friction values in the range of 0.02–0.2 as compared to 0.4–1.0 for uncoated Al. There is tremendous improvement in the wear life of the pin, with UHMWPE + PFPE film giving wear life approximately twice to thrice higher than that with only UHMWPE film. A thin polymer film is transferred to the disk surface during sliding providing very long-term wear life (continuous low coefficient of friction) despite visual removal of the film from the pin surface. The present films will have applications in gears and bearings as solid or boundary lubricants for automotive and aerospace component.     

Tribochemistry in the analytical UHV tribometer

The knowledge of tribochemical reactions in boundary lubrication in the presence of lubricant additives is fundamental in order to improve chemical engineering of new molecules, multifunction compounds and to predict interactions between these additives. Experiments with in lubro, ex situ or post-mortem analyses are difficult and even dangerous to exploit because of numerous artefacts. We introduce two special approaches to simulate boundary lubrication tribochemistry. Basically, these approaches use a dedicated analytical UHV tribotester allowing in situ AES/XPS analysis of both counterfaces and introduction of partial pressure of gases during friction. The first model experiment is UHV friction on previously formed tribofilms from a lubricated test. The second experiment is gas phase lubrication with ethyl phosphate. The results reveal some fundamental aspects of the origin of friction-reduction by transfer of MoS₂ single sheets. The reaction of friction-activated nascent surfaces with gases is also emphasised.     

The friction and wear properties of nanometre SiO2 filled polyetheretherketone

Nanometre SiO₂ filled-polyetheretherketone (PEEK) composite blocks with different filler proportions were prepared by compression moulding. Their friction and wear properties were investigated on a block-on-ring machine by running a plain carbon steel (AISI 1045 steel) ring against the composite block. The morphologies of the wear traces and the transfer film were observed by scanning electron microscopy (SEM). It was found that nanometre SiO₂ filled-PEEK exhibited considerably lower friction coefficient and wear rate in comparison with pure PEEK. The lowest wear rate was obtained with the composite containing 7.5 wt.% SiO₂. The SEM pictures of the wear traces indicated that with the frictional couple of carbon steel ring/composite block (fillec with 7.5 wt.% filler), a thin, uniform, and tenacious transfer film was formed on the ring surface. It was inferred that the transfer film contributed largely to the decreased friction coefficient and wear rate of the filled PEEK composites.     

Tribological Properties of Films Formed by the Reaction of Carbon Tetrachloride with Iron

The tribological properties of halide films grown on iron by reaction with carbon tetrachloride vapor at a temperature of 617 K and a pressure of 1.7 Torr are compared, in ultrahigh vacuum, with FeCl₂ films evaporated onto the surface. It is found that the reactively formed film has a slightly lower limiting friction coefficient than the evaporated layer (~0.06 compared to ~0.08), which may be due either to the diffusion of some carbon into the substrate or the formation of a more oriented layer when this is formed reactively. The major difference between the reactively grown and evaporated film is that the evaporated layer attains the minimum friction when ~40 ? of FeCl₂ has been evaporated, while the reactively formed layer has a minimum friction coefficient when a film of 6±2 ? has been deposited. In the case of the evaporated FeCl₂ film, the growth of second and subsequent layers proceeds before the first layer is complete. It has been shown that the friction coefficient reaches its minimum value after completion of the first monolayer, a process that is complete after the evaporation of ~40 ? of FeCl₂. In the case of the film formed by reaction with CCl₄, the halide film grows directly on the surface implying that the FeCl₂ monolayer thickness is ~6 ?. This value is in good agreement with the layer thickness in bulk ferrous chloride.     

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.     

Large friction anisotropy of a polydiacetylene monolayer

Friction force microscopy measurements of a polydiacetylene monolayer film reveal a 300% friction anisotropy that is correlated with the film structure. The film consists of a monolayer of the red form of N‐(2‐ethanol)‐10,12‐pentacosadiynamide, prepared on a Langmuir trough and deposited on a mica substrate. As confirmed by atomic force microscopy and fluorescence microscopy, the monolayer consists of domains of linearly oriented conjugated backbones with pendant hydrocarbon side chains above and below the backbones. Maximum friction occurs when the sliding direction is perpendicular to the backbones. We propose that this effect is due to anisotropic film stiffness, which is a result of anisotropic side chain packing and/or anisotropic stiffness of the backbone itself. Friction anisotropy is therefore a sensitive, optically‐independent indicator of polymer backbone direction and monolayer structural properties. This revised version was published online in September 2006 with corrections to the Cover Date.     

Effect of densification and TiB2 reinforcement on the wear of molybdenum disilicide

Wear tests were done in a pin‐on‐disc machine by sliding MoSi₂ pins against hard‐steel discs in a normal load range of 5–140 N and a speed of 0.5 m/s under nominally dry conditions in the ambient. The specific wear rate of the pin undergoes two transitions: severe to mild at low load and mild to severe at high load. The mild‐wear domain is distinguished by the formation of a protective mechanically mixed layer of steel and its oxides, transferred from the counterface in particulate form. Increasing the hardness by densification and TiB₂ reinforcement lowers the specific wear rate and expands the mild‐wear load domain. However, even when the volume wear rate is normalised with respect to the real contact area (load/hardness) the non‐dimensional wear factor is still seen to decrease with densification and reinforcement. This indicates that fracture toughness may also play an important role in determining the wear‐resistance of these materials. The surface coverage on the pin by the mechanically mixed layer increases with densification and reinforcement. This revised version was published online in July 2006 with corrections to the Cover Date.