Chemistry of Antiwear Films from Ashless Thiophosphate Oil Additives

X-ray absorption near-edge structure (XANES) spectroscopy has been combined with atomic force microscopy (AFM) to investigate the interaction of ashless thiophosphate oil additives on steel. Both mono- and dithiophosphates were studied and compared with one another in terms of chemistry and tribological performance. XANES revealed that, thermally, all three thiophosphate additives behaved similarly with steel to form a thermal film at temperatures of 150 °C. The thermal films all consisted of a layered structure comprised of Fe(II) polyphosphate and FeSO₄ in the bulk and iron polyphosphate of various chain length towards the surface. Tribochemical films generated at 5min, 1 h, and 6 h of wear testing revealed that for all three additives, the phosphorus chemistry of an antiwear (AW) film remained chemically consistent throughout all rubbing times. This suggests that the phosphorus chemistry of the AW film is determined in the initial stages of tribofilm formation. The iron polyphosphate chain length remained uniform throughout the AW film with short chain iron polyphosphates found both at the surface and in the bulk of the films. Mild AW conditions produced several different forms of sulfur at the various stages during wear testing. S K-edge XANES spectra for the 5-min tribofilms (both total electron yield and fluorescence yield) showed oxidized and reduced forms of sulfur throughout the films for all three additives. Over extended periods of rubbing (6 h), the more thermodynamically stable product, FeSO₄, was produced and became the major constituent of the tribofilms formed. Iron sulfate was present throughout the films with only traces of reduced sulfur present.AFM imaging of the AW films revealed that the morphology of the films varied from additive to additive and changed over the duration of wear testing. Generally, the AW films were composed of elongated pads orientated in the sliding direction. As rubbing continued, the pads of each AW film became more homogeneous. The larger pads of AW film appeared to have supported most of the load throughout the course of wear testing, resulting in better AW protection to the metal over increased periods of rubbing     

The Correlation of Microchemical Properties to Antiwear (AW) Performance in Ashless Thiophosphate Oil Additives

X-ray absorption near-edge structure (XANES) spectroscopy at macro-scale (mm2) and X-ray photoelectron emissions microscopy (X-PEEM) at micro-scale (m2) have been used to investigate the chemistry and spatial distributions of chemical species in tribochemical films generated from ashless thiophosphate oil additives on steel. Two different ashless thiophosphate additives were used: a triaryl monothiophosphate (MTP) and a dialkyldithiophosphate (DTP). Atomic force microscopy (AFM) and secondary electron microscopy (SEM) were also used to investigate the thickness and the topography of the tribofilms. Macro-scale XANES analysis showed that both ashless thiophosphates reacted with the steel surface to produce short to medium chain polyphosphates as the main constituent and sulfur species as minor component. From the PEEM experiment, it was found that the DTP tribofilm was microchemically heterogeneous, with areas of varying degrees of polyphosphate chain length. Conversely, MTP formed a tribofilm microchemically homogeneous, with areas comprised of only short chain polyphosphates. From, the different areas of polyphosphate chain length within the DTP tribofilm, colour-coded polyphosphate distribution map was generated. AFM, X-PEEM and SEM revealed that the DTP film was thicker and was composed of AW pads that were wider in area than MTP. This resulted in a smaller wear scar width (WSW) value for DTP. This is the first time that all these analytical techniques have been combined to better understand the nature of the tribofilms from ashless additives. We have concluded that an ideal AW film is comprised of a thick film with pad-like structures that are wider in area and microchemically heterogeneous, with areas of varying polyphosphate chain length.     

Combination of ashless antiwear additives with metallic detergents: interactions with neutral and overbased calcium sulfonates

The interactions of neutral and overbased calcium sulfonate detergents with ashless thiophosphate oil additives under boundary lubrication were studied. The ashless additives used were neutral and acidic dialkyldithiophosphate (DTPs) and neutral triaryl monothiophosphate (MTP). This study uses three surface analytical tools to provide elemental and chemical information at the surface and in the bulk of the derived tribochemical films. The elemental composition of the tribofilms was studied using X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray analysis (EDX) (combined with scanning electron microscopy (SEM)). Corresponding P and S X-ray absorption near edge structure (XANES) spectroscopy was also used to provide further insight into the chemical composition of the films. SEM images of the derived tribofilms revealed that each film had distinct topographical features associated with it. XPS and EDX revealed that when oil is blended with calcium sulfonate, considerable amount of calcium is incorporated into all the tribochemical films. The phosphorus content of the tribofilm was reduced substantially when the overbased detergent was combined with MTP additive. XANES spectroscopy of the P L-edge provided direct evidence for the formation of calcium phosphate in tribofilms from the ashless additives in combination with the detergent.S K-edge revealed that sulfate is the main sulfur species formed in the bulk for all three tribofilms in the presence of the neutral detergent while a mixture of sulfite and sulfide species are formed when the overbased was used. S L-edge XANES showed that calcium sulfonate has undergone some oxidation at the surface. A more antagonistic effect was observed for MTP, with the formation of a very thin phosphate film.Tribological performance was also evaluated. Surprisingly, combination of the neutral detergent with any of the AW additives did not result in any significant change in wear to the substrate. For MTP plus neutral detergent, the thinner phosphate film produced, combined with very little change in wear protection confirms that, not only is the tribochemistry dominated by calcium sulfonate, but also confirms the anti-scuffing and AW properties that are associated with it as well. Even more surprising, was the significant decrease in wear when the overbased detergent is used. This illustrates not only that the tribochemistry was dominated by the detergent, but also the exceptional AW properties of calcium carbonate.     

Study of the Chemistry of Films Generated from Phosphate Ester Additives on 52100 Steel Using X-ray Absorption Spectroscopy

X-ray absorption near-edge structure spectroscopy (XANES) has been used to investigate the chemistry and thickness of thermal and antiwear (AW) films generated on steel from oil solutions containing phosphate ester additives. DPP, a diaryl phosphate, reacted with steel to form a thermal phosphate film at lower temperatures than TPP, a triaryl phosphate and Irgalube 349, an amine phosphate. This phosphate film formation at lower temperatures resulted in better wear protection to the metal in tribochemical experiments, as indicated by a smaller wear-scar measurement for oil solutions containing the DPP additive. For TPP, a brief period of wear to the metal was necessary to initiate the tribochemical reaction between the additive and substrate. Once the tribochemical reaction begins, TPP is able to generate a tribochemical film of relatively the same thickness and chemistry as DPP. Irgalube 349 generated the thickest thermal films at temperatures greater than 150 °C, significantly thicker than any of the films generated from DPP and TPP. The substantial difference in thickness is believed to be due to the availability of alkyl/ammonium cations which enables continued growth of the phosphate film.     

X-Ray Absorption Spectroscopy and Morphology Study on Antiwear Films Derived from ZDDP Under Different Sliding Frequencies

X-ray absorption near-edge structure (XANES) spectroscopy has been used to characterize the chemistry of antiwear (AW) films generated from mineral base oil containing a zinc dialkyl dithiophosphate additive. These films were formed on rubbed steel surfaces with a reciprocating boundary contact using different sliding frequencies. The phosphorus L-edge XANES spectra show that these films have slightly different chemical natures. Longer chain polyphosphates were present on the steel surface prepared at the higher sliding frequencies. The surface morphology of these films was investigated using atomic force microscopy. These images show that the surface morphology of the AW films changes with the sliding frequency. Round and bigger antiwear pads were formed at a lower frequency while higher frequencies resulted in thinner films and flattened surfaces. Nanomechanical properties of these antiwear films were investigated by nanoindentation measurement and the elastic moduli extracted from force–displacement (f–d) curves are similar for all antiwear films, 100 ± 10 GPa.     

Study of surface films of overbased sulfonates and sulfurized olefins by X-Ray Absorption Near Edge Structure (XANES) spectroscopy

The X-Ray Absorption Near Edge Structure (XANES) spectroscopy technique has been successfully applied to complex matrices such as tribological films, coal, DLC films and, where other instrumental analytical techniques are less sensitive for molecular analysis. Four-ball tests were performed for lubricating oils containing the synergistic combination of overbased sulfonate (calcium and magnesium) and sulfurized olefin. The surface films were analyzed by XANES using C K-edge, Ca L-edge and S L- and K-edge. Using this technique we were able to differentiate the carbonate from organic carbon in C K-edge spectra, as well as, determining the difference between FeS, FeS_2, RSO₃⁻ and SO₄²⁻ in the sulfur spectra. It was found while the sulfurized olefin reacts very strongly with the substrate to form FeS, the overbased calcium sulfonate and overbased magnesium sulfonate do not react strongly with the substrate without sulfurized olefin present. There is evidence to suggest that the overbased sulfonate promotes decomposition of the sulfurized olefin on the surface to form both CaSO₄ and FeS, which improves the EP performance of the lubricant.     

Tribological study and mechanism of B–N and B–S–N triazine borate esters as lubricant additives in mineral oil

The tribological study of N-containing heterocyclic borate esters as lubricating additives had been the research hotspot. In this work, B–N and B–S–N triazine borate esters were synthesized and their antiwear/extreme pressure (AW/EP) properties were studied. Results showed the synthetical additives had good AW performance. However, B–S–N triazine borate ester showed excellent EP property while B–N triazine borate ester hardly owned EP property. The hydrolytic stability of borate ester additives was improved by the formation of coordination of nitrogen to boron. The XANES spectroscopy analysis showed that there was a layer of borate–oxygen–iron inorganics in the tribofilms. The existence of iron sulfate and iron sulfide guaranteed good AW/EP properties of B–S–N triazine borate ester additive in mineral oil.     

Thermal Effect on Atomic Friction with Deformable Substrate

A novel borate ester containing heterocyclic group, 2,5-bis((2-((6-octadecyl-1,3,6,-dioxazaborocan-2-yl)oxy)propyl)thio)-1,3,4-thiadiazole (BDOT), was prepared and characterized. Its tribological properties and synergistic effect with zinc dialkyl dithiophosphate were evaluated using a four-ball tribometer. The results show that the novel borate additive possesses excellent anti-wear and friction-reducing properties compared with the performance of ZDDP. BDOT combined with ZDDP has a synergistic effect on the tribological properties, especially for the friction-reducing performance. The chemical state of nitrogen, boron and sulfur in thermal films and tribofilms was analyzed by XPS and XANES. XPS analysis suggests that the additive forms a protective film on the rubbing surfaces which is composed of B₂O₃, BN, FeSO₄, FeS₂ and Fe₂O₃. However, the B K-edge XANES shows that no BN was detected in the film. The synergistic effect between BDOT and ZDDP may be due to the formation of right concentration of FeS and FeSO₄ in the tribofilm.     

Study of the tribological behavior of S-(carboxylpropyl)-N-dialkyl dithiocarbamic acid as additives in water-based fluid

There has been a growing concern for the use of water-based fluids because of the worldwide interest in environmental issues. This has promoted the research and use of water-soluble additives as environmental friendly lubricants. A kind of potential water-soluble additive, S-(carboxylpropyl)-N-dialkyl dithiocarbamic acid was prepared in this work. The friction and wear behaviors of the synthesized compounds as an additive in water-based liquid were evaluated with a four-ball tester and a ring-on-block rig. The wear scar morphology of the ball and the chemical nature of the antiwear films generated on the steel counter face were investigated with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It was found that the synthesized additives had excellent antiwear, load-carrying and extreme pressure performance. The additive reacted with the counter-face metal and generated a surface protective film consisting of FeS, FeS₂, FeSO₄ and an absorbed compound containing N and acid.     

Study of interaction of EP and AW additives with dispersants using XANES

The chemical interaction of two kinds of dispersants (bis-succinimide dispersant and borated bis-succinimide dispersant) with four kinds of antiwear (AW) and extreme pressure (EP) additives (zinc dialkyldithiophosphate, dialkyldithiophosphate ester, diphenylphosphate ester and dialkyldithiocarbamate) has been investigated under different contact pressures. The chemical compositions of the tribofilms have been studied by B, N, P and S X-ray absorption near edge structure (XANES) spectroscopy. The N K-edge XANES analysis has been used to follow the reaction pathway of amine and imide functional groups in the dispersants and their interactions with EP and AW additives. It has been found that AW additives react with amine to form amine phosphate at low load. However, at high load, there is a good evidence for the formation of a nitrate phase in the tribofilms, the first direct observation of oxidative dispersant loss in the rubbing contact. On the other hand, EP additives behave differently and in general are less reactive. The B K-edge XANES has been employed to follow the interaction of borated dispersant with the EP and AW additive. In general, boron originally in the trigonal coordination, is converted to a tetrahedral coordination form in the process of tribofilm formation.     

XPS and XANES characteristics of tribofilms and thermal films generated by two P- and/or S-containing additives in water-based lubricant

Two phosphates were synthesized and their tribological properties as water-soluble lubricant additives were evaluated by using four-ball tester. The micro/nano-scale chemical characteristics of tribofilms and thermal films formed from these additives in different conditions were explored by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy. The results show that the additives have better anti-wear and friction reducing properties than the oleate solution at higher load. Surface analysis results indicate that tribofilms are mainly composed of absorbed layer and chemical reactant layer, in which phosphorus exists in the form of adsorbed molecule, phosphate or polyphosphate, and sulfur in the form of alkyldisulfide, sulfide and sulfate. As to the thermal films, phosphate (or polyphosphate) and sulfate are detected as the main components. The anti-wear and friction-reducing performances can be ascribed to the formation of films on the metal surface, and the mechanism of the process of molecules adsorption, new compounds production through tribochemical reactions, film formation and destruction.     

Tribological behaviour of antiwear additives used in hydraulic applications: Synergistic or antagonistic with other surface-active additives?

This paper examines the friction and antiwear (AW) properties using SRV (Schwing–Reib–Verschleiss) tribometer and film-forming properties using atomic force microscope (AFM) of one simple model formulation containing solely AW additive and seven oils containing mixture of additives including three zinc-based packages (ZP), ZP with additional AW additives, ZP with extreme pressure (EP) additives, ZP with viscosity index improvers (VII) and one zinc-free ashless package in steel/steel contacts. VII-containing oil show lower boundary and mixed friction coefficients than the other oils. Although all AW additive-containing oils formed tribofilms, AW properties of ZPs appear to be affected antagonistically by EP additives while synergistically by VII. Zn-free additives investigated in this study show higher wear than ZPs.     

Tribological Behavior of Some Long-Chain Dimercaptothiadiazole Derivatives as Multifunctional Lubricant Additives in Vegetable Oil and Investigation of their Tribochemistry Using XANES

A series of novel long-chain dimercaptothiadiazole derivatives are prepared and used as antiwear (AW) and extreme pressure (EP) additives in vegetable oil, and their tribological performance is tested by using a four-ball tester. In order to understand the friction process further, X-ray absorption near edge structure spectroscopy is adopted to analyze the chemistry of tribofilms under AW/EP regime, and meanwhile thermal films are also considered for comparison. These derivatives are capable in improving the tribological characteristic of the base stock, and disubstituted derivatives are more effective than other derivatives. Though disubstituted derivatives and disubstituted polysulfur derivatives all fail in improving tribological performance at 0.1 wt%, they are still helpful at other additive concentrations. All these long-chain thiadiazole derivatives, in particular the disubstituted polysulfur ones, are good at improving the EP characteristic of the base colza oil. Thermal films generated from these derivatives are composed of ferrous sulfate and a small amount of adsorbed organic sulfide. During the heating process, these long-chain derivatives easily undergo thermal oxidation to generate high-valent sulfate on the metal surface. Ferrous sulfide is the main component of tribofilms generated by these derivatives, while ferrous sulfate in these films almost vanishes at 1.0 wt%. These long-chain derivatives tend to react with metal surface to generate low-valent sulfide under rubbing conditions. On the other hand, ferrous sulfide is also the main component of EP films generated by monosubstituted derivatives and disubstituted polysulfur derivatives at 1.0 wt%. But the EP films formed by disubstituted derivatives are composed of ferrous sulfide and ferrous sulfate.     

A multi-technique characterization of ZDDP antiwear films formed on Al (Si) alloy (A383) under various conditions

The simulation of the lubrication of aluminum–silicon (Al–Si) alloy cylinder-bore conditions is an important goal in automotive tribology. This study describes the use of X-ray absorption near edge structure (XANES) to determine the macro-chemistry of zinc-dialkyl-dithiophosphates (ZDDPs) antiwear (AW) films formed on A383, an Al-Si alloy. The temperature dependence of the chemistry and mechanical properties were examined using X-ray photoelectron emission microscopy (X-PEEM), and imaging indentation techniques. Our findings suggest that ZDDPs break down to form polyphosphate glasses, which have different chemical natures and depend on the underlying substrate. Furthermore, the chemical nature of the films appears temperature dependent on both the macro- and micro-scale. Not only are the chemical species different, but the mechanical properties also differ, depending on the region upon which an AW pad is formed. Through the use of focused ion beam (FIB) milling, we can determine the film thickness, which was previously estimated from the P K-edge XANES areal density of samples with known thicknesses.     

Studies on ZDDP Thermal Film Formation by XANES Spectroscopy, Atomic Force Microscopy, FIB/SEM and 31P NMR

X-ray absorption near edge structure (XANES) spectroscopy has been used to characterize the chemistry of thermal films on steel samples, which were generated from a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive. These films were formed at 150 °C by immersing steel coupons in ZDDP oil solutions. The phosphorus L-edge XANES spectra show that these films are composed of polyphosphates, unreacted ZDDP and other thiophosphate intermediates. Phosphorus K-edge FY XANES was used to monitor the thickness of these films, and the data are consistent with thickness derived by focussed ion beam (FIB) milling and SEM imaging. The sulphur K-edge TEY and FY XANES spectra show that these films are composed of different sulphur components, which depend upon the formation times. The surface morphology of these films was investigated using atomic force microscopy (AFM). These images show that the surface morphology of the thermal films changes with the formation time. 31P NMR spectra show that both primary and secondary ZDDP decomposes gradually at 150 °C.     

Effects of Sulfur Additive EP in Ester Coolants during Friction with CBN

A study was undertaken to investigate the effects of the EP additives during tribological tests using a CBN tool against steel. Ester oil with and without sulfur additive were used as lubricants in a tribometer. Tribochemical interactions between the S additive and steel have been investigated under boundary lubrication conditions by SEM and EDX analysis. The relative abundance of different elements on the surface of the CBN tools, which are present in the workpiece material such as Fe (iron) and Cr (chromium), suggests that adhesion occurred when the ester oil without sulfur additive was tested. Tribochemical interactions between the additive and the steel could be observed when using the ester oil containing the sulfur additive. These interactions contribute to the formation of a uniform layer on the CBN tool. This layer is composed by S (sulfur), Fe, and O (oxygen). The presence of these elements indicate that FeO (iron oxide) and FeS (iron sulfide) were formed.     

The Tribological Chemistry of Novel Triazine Derivatives as Additives in Synthetic Diester

Two novel triazine derivatives 2-tris(2-ethylhexyl)-3,3′,3″-(1,3,5-triazine-2,4,6-triyl)-tris(sulfanediyl)tripropanoate (TE TST) and 2-ethylhexyl-3-(4,6-dimercapto-1,3,5-triazin-2-ylthio) propanoate (EDTYP) were synthesized. Their tribological properties in synthetic diester were evaluated using a four-ball tribometer, and the thermal films and tribofilms were investigated using X-ray absorption near-edge structure (XANES) spectroscopy. The copper corrosion-inhibiting performance was explored as well. The additives can improve the extreme pressure performance of base stock. TETST displays good antiwear property and EDTYP possesses excellent friction-reducing ability. Surface analysis indicated that the thermal films are exclusively composed of FeSO₄, and the tribofilms are constituted by FeS, FeS₂, and FeSO₄. The mechanism obtained from the XANES analysis fit well with the results of tribological tests.     

The Tribological Chemistry of the Oil Blends of Zinc Dialkyldithiophosphate with 2-Mercaptobenzothiazole Derivatives

X-ray absorption near-edge spectroscopy at the phosphorous and sulfur edges was used to identify the chemical species in thermal films and antiwear films on the macroscale. For the thermal films, it was found that the introduction of the additive MBTT/MBTA to the base oil, zinc dialkyldithiophosphate (ZDDP), tended to retard the formation of the polyphosphate, and has no effect on the thickness of the films. The topmost surface thermal films may be mainly comprised of some new compounds generated from the interaction of ZDDP with the antiwear additives MBTT/MBTA, along with a small amount of unchanged ZDDP, the sub-surface, and the bulk were mainly comprised of Zn phosphate, along with an amount of ZnS. For the antiwear films, the introduction of the additive MBTT/MBTA to the base oil, ZDDP, reduces the chain length of polyphosphate, which the N-containing decomposed products of 2-mercaptobenzothiazole derivatives are responsible for. It is very clear that MBTT or MBTA has indeed interacted with ZDDP to form new phosphate in the overall antiwear films. The topmost surface antiwear films were mainly comprised of short-chain polyphosphate, the sub-surface and the bulk may be mainly comprised of Zn phosphate and ZnS.     

Tribological behavior and tribofilm composition in lubricated systems containing surface-capped molybdenum sulfide nanoparticles

The tribological behavior of surface-capped MoS₃ nanoparticles (nano-MoS₃) in hydrocarbon oils was studied both alone and in combination with ZDDP. It was found that the nano-MoS₃ additive alone demonstrates pro-wear properties and decreases the friction coefficient only at high temperatures. The combination with ZDDP demonstrates synergism in antiwear and antifriction activity even at low ZDDP content. X-ray Absorption Near Edge Structure (XANES) spectroscopy at the sulfur, molybdenum and phosphorus edges was used to identify the chemical species in tribochemical films. It was established that the nano-MoS₃-formed tribofilms are composed of oxidized sulfur and molybdenum species while tribofilms formed by combination with ZDDP are composed of phosphate layers incorporating MoS₂-type fragments providing friction reduction.     

The Effect of Steel Hardness on the Performance of ZDDP Antiwear Films: A Multi-Technique Approach

X-ray absorption near-edge structure (XANES) analysis has been used to characterize the chemistry of antiwear films formed in a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive. These films were formed by rubbing the AISI 1095 steel samples under a reciprocating boundary contact. The steel samples were tempered to produce different Vickers hardness values. The phosphorus L-edge XANES spectra show that these films differ slightly in their chemical nature, with longer chain polyphosphates being formed on samples with higher hardness value. The surface morphology of the films was investigated using Atomic force microscopy (AFM) and the film thickness was probed by Focussed ion beam and Scanning electron microscopy (FIB/SEM) techniques. Furthermore, the nanomechanical properties of these antiwear films were investigated by nanoindentation methods. Tribological measurements of the coefficient of friction (μ) and wear scar width (WSW) indicate that the poorest antiwear film was formed on the softest substrate, which exhibited the largest WSW and the highest average μ. FIB/SEM images show that the thicknesses of the antiwear pads and the degree of damage on the substrates both change with the hardness value of the samples.