Studies on ZDDP Anti-Wear Films Formed Under Different Conditions by XANES Spectroscopy,Atomic Force Microscopy and 31P NMR

Antiwear (AW) films, generated from a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive, were studied as a function of formation temperature, load and rubbing time. The surface morphology of these films was investigated using atomic force microscopy (AFM), and surface roughness calculated for the observed differing surface morphologies. The morphology of the films is heterogeneous for all the tested conditions, but the surface roughness is dependent on the rubbing condition. X-ray absorption near edge structure (XANES) spectroscopy has been used to characterize the chemistry of these films, and the intensity of the phosphorus K-edge was also used to monitor their thickness. The thickness of these films is in the range of 10–90 nm depending on the running conditions. Phosphorus L-edge spectra show that these films have a similar chemical nature with variable polyphosphate chain-lengths. 31P NMR was used to study the decomposition of ZDDP in the residual oils. The spectra show that the primary and secondary ZDDP react differently under the various conditions. The tribological characteristics of these AW films were probed by measuring the coefficients of friction (μ) and the wear scar width (WSW) of the counter faces. μ is highly related to the applied load and the results of WSW measurements show that the wear performance is related to all the tested parameters, temperature, load and rubbing time.     

Tribofilms generated from ZDDP and DDP on steel surfaces: Part 2, chemistry

The chemical constitution of tribofilms, generated from zinc dialkyldithiophosphate (ZDDP) and ashless dialkyldithiophosphate (DDP), has been examined by X-ray Absorption Near Edge Structure (XANES) spectroscopy. The identification of spectral features and interpretation of the results for P, O, Fe, and S species are given, allowing an overall mechanism to be deduced. The role of Fe in these films was investigated in some detail using P L-edge, O K-edge and Fe L-edge XANES spectra. From the P L-edge XANES spectra, the DDP films are uniformly very short chain iron polyphosphates. In contrast, the ZDDP films are formed initially as short chain polyphosphates; but after more rubbing, a bilayer phosphate film is formed with long chain Zn polyphosphates on the surface and shorter chain in the bulk of the film. The O K-edge XANES spectra show that there is, as expected, more Fe in the DDP phosphate films than in the ZDDP phosphate films. The S K-edge spectra of ZDDP films show the presence not only of ZnS as previously observed, but also the presence of FeS for the first time in the early stages of film formation. The predominant S species in the DDP films is FeS.     

Study of the Interaction of ZDDP and Dispersants Using X-ray Absorption Near Edge Structure Spectroscopy—Part 1: Thermal Chemical Reactions

The interactions of ZDDP and different dispersants have been investigated both in oil solutions and on steel substrates at 150–185°C. X-ray absorption near edge structure (XANES) spectroscopy at P and S L-edge and K-edge has been used to identify the chemical species both in solution and on the surface of the steel. It was found that noticeable ZDDP decomposition in solution starts at 175°C when no dispersant is present. In contrast, thermal oxidative films begin to form on the steel at 150 °C in the same solution. The products of decomposition in solution and in the film are phosphates and sulfides. N K-edge XANES spectroscopy has also been utilized to identify the reaction of the dispersant with the steel surface and ZDDP. The results show that dispersants enhance the decomposition of ZDDP in oil solutions as well on the steel surface. Dispersants, on their own, react/adsorb with the steel surface at 150–175 °C and also interact with ZDDP to form new products. Depending on the composition of the dispersants, the product is different.     

Antiwear film formation of neutral and basic ZDDP: influence of the reaction temperature and of the concentration

Both synchrotron radiation-based techniques (XANES) and transmission electron microscopy (EDX, EELS) are used to draw a comparison of antiwear and thermal films generated from neutral and basic ZDDP salts. Antiwear films were created in a pin-on-flat wear machine and the wear debris was collected. The analysis of the tribofilms did not show any substantial difference between neutral and basic ZDDPs. The wear scar diameter and the P and S chemical environment in the tribofilm were very similar. The chemical analysis of the wear debris revealed differences in the chemical composition. Wear debris from basic ZDDP seems to be mostly composed either of unreacted ZDDP or of a linkage isomer of ZDDP (LI-ZDDP), and zinc polyphosphate; whereas the wear debris as far as neutral ZDDP is concerned seems to be exclusively composed of zinc polyphosphate (and sulphur species). More iron was also detected in the wear debris with basic ZDDP – possibly an indication of the iron content of the tribofilm. Differences in chemical structure could also be detected in the thermal films. While neutral ZDDP reacted with the surface to form polyphosphates at 150°C, the same reaction products were obtained with basic ZDDP at 175°C. The concentration of ZDDP in oil is thought to be the main parameter to explain the differences in the thermal film formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interaction of ZDDP with Borated Dispersant Using XANES and XPS

The thermochemical reaction and tribochemical reaction of zinc dialkyldithiophosphate (ZDDP), a borated dispersant, and the mixture of ZDDP and borated dispersant on steel surfaces were investigated. Both pin-on-disk and ball-on-disk were used to generate tribofilms. The chemical state of nitrogen, boron, phosphorus, and sulfur in heated oil solutions, thermal films, and tribofilms were analyzed by X-ray absorption near edge structure (XANES) spectroscopy to obtain the chemical nature of species on the surface and in the bulk of the films. High-resolution X-ray photoelectron spectroscopy (XPS) has also been used to analyze boron (B) in tribofilms.

The borated dispersant in base oil by itself yields good anti-wear behavior. This can be attributed to the presence of boron in the dispersant. The wear scar widths (WSW) for ZDDP alone, and in combination with the dispersant, yield similar results within the experimental error. It was found that the borated dispersant facilitates the decomposition of ZDDP and the formation of phosphate in tribofilms and thermal films. B K-edge XANES shows that boron has a trigonal coordination in the untreated additive, but the coordination changes partially to a tetrahedral coordination in the tribofilm upon rubbing. No BN was detected in the film analyzed by B K-edge or N K-edge. Boron 1s XPS also did not show the presence of BN in the film.     

Solution decomposition of zinc dialkyl dithiophosphate and its effect on antiwear and thermal film formation studied by X-ray absorption spectroscopy

A detailed study was undertaken to investigate the effect of ZDDP oil solution chemistry changes due to thermal decomposition, on antiwear and thermal film chemistries, film thickness and wear. P and S K- and L-edge X-ray absorption near edge structure (XANES) spectroscopies were used to characterize film chemistry, and 31-P NMR spectroscopy was used to monitor the ZDDP oil solution chemistry. P L-edge XANES results of antiwear films prepared from ZDDP oil solutions preheated at 150°C for various lengths of time, showed a decrease in polyphosphate chain length as ZDDP thermal solution decomposition progressed. Film thickness and wear increased with increasing ZDDP oil solution preheating time (decomposition). Antiwear films formed from ZDDP oil solutions preheated at a higher temperature (200°C) for 1 and 3 h, yielded thinner films and showed catastrophic wear. 31-P NMR spectra showed that no oil soluble P containing species were left in solution after heating at 200°C for 1 h and yet the 200°C, 6 h antiwear film was found to be as thick as that generated from previously unheated solution. Wear was comparable to that obtained by using base oil alone. These films were found to be of short chain polyphosphate structure. ZDDP oil solution chemistry was also shown to have an effect on the chemistry of thermally generated films. Film chemistry changed with ZDDP oil solution heating time. A linkage isomer of ZDDP is proposed as an important precursor for film formation after analysis and comparison of an oil insoluble ZDDP decomposition product with the thermal and antiwear film chemistries. As with the related antiwear films, thermal film thickness was also shown to increase dramatically when ZDDP decomposition in solution increased. An overall mechanism for film formation, taking into account the ZDDP linkage isomer and the deposition of colloidal polyphosphate material, is proposed.     

Tribofilms generated from ZDDP and DDP on steel surfaces: Part 1, growth,wear and morphology

The growth and morphology of tribofilms, generated from zinc dialkyldithiophosphate (ZDDP) and an ashless dialkyldithiophosphate (DDP) over a wide range of rubbing times (10 s to 10 h) and concentrations (0.1–5 wt% ZDDP), have been examined using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy at the O, P and S K-edges and the P, S, and Fe L-edges. The physical aspects of the growth and morphology of the tribofilms will be presented in Part I and the chemistry of the films will be discussed in Part II. The major components of all films on 52100 steel are Zn and Fe phosphates and polyphosphates. The average thickness of these phosphate films has been measured using P K-edge XANES and XPS profiling. For ZDDP, a very significant phosphate film (about 100 Å thick) forms after 10 s, while film development for DDP is substantially slower. However, for both additives, the average film thickness increases to 600–800 Å after 30 min of rubbing, before leveling off or decreasing. The antiwear properties of pure ZDDP and in combination with DDP at different rubbing times and concentrations have also been examined. It was found that under all conditions, the performance of ZDDP as an antiwear agent is superior to that of DDP. However, DDP has no adverse effect on the performance of ZDDP when the two are mixed. The AFM results show that ZDDP forms larger and better developed “pads” than DDP at short rubbing times. At longer rubbing times, both films become more uniform. For the 1 h ZDDP films, the film thickness is surprisingly independent of the ZDDP concentration from 0.1 to 5 wt% ZDDP. The film thickness is also independent of the ratio of ZDDP/DDP concentrations.     

Characterization of tribofilms derived from zinc dialkyldithiophosphate and salicylate detergents by X-ray absorbance near edge structure spectroscopy

Phosphorous and sulfur L- and K-edge X-ray absorption near edge structure (XANES) spectra were recorded to characterize the surface chemistry of the tribofilms derived from a commercial zinc dialkyldithiophosphate (ZDDP) and its blends with overbased calcium and magnesium salicylate detergents. The results show that the chemical structure of the tribofilms generated from the mixture of ZDDP and detergents is different from that of the tribofilm derived from ZDDP alone. However, the two kinds of detergents inhibit ZDDP from forming tribofilm, producing thinner polyphosphate films. Though XANES analysis does not provide definite evidence to the existence of magnesium element in the tribofilms, it is likely that calcium or magnesium has been incorporated therein. Moreover, ion exchange reaction and the formation of zinc polyphosphate film may occur simultaneously during sliding. However, calcium or magnesium (poly)phosphates do not contribute to reduce friction and wear of a steel–steel pair.     

Mechanisms of tribochemical film formation: stabilityof tribo- and thermally-generated ZDDP films

Phosphorus L-edge and sulphur L-edge X-ray absorption near-edgestructure (XANES) spectroscopy has been used to characterize thechemical nature of tribochemical and thermo-oxidativelygenerated films from a sec-ZDDP antiwear agent. The chemicalstability of the films has been investigated by rubbing the filmsin base oil without ZDDP. The P L-edge XANES spectra have shownthat the thermal film and in particular the tribo-films are verystable after rubbing in the base oil for a long period of time.The wear scar measurements indicate that best results are givenif the coupon and pin is coated with a tribo-film and then rubbedin oil containing ZDDP.     

X-ray absorption near-edge structure analysis of the chemical environment of zinc in the tribological film formed by zinc dialkyl dithiophosphate decomposition on steel

Calculation of X-ray absorption near-edge structure (XANES) has been used to investigate the chemical nature of zinc in thermal films formed on the surfaces of steel coupons by the additive zinc dialkyl dithiophosphate (ZDDP) in oil solution. Carbon K, oxygen K, and zinc L edge XANES spectra were used to characterize the thermal films and a model film formed by addition of cumene hydroperoxide (CHP) to the ZDDP. Thermal films formed by heating at up to 100 °C for 5 h showed little change from unreacted ZDDP. At 160 °C for 5 h, the ZDDP underwent thermal solution decomposition with similarities to the oxidation induced by CHP. The Zn L edge XANES spectra were compared to calculated spectra of the model surface species ZnO and ZnS in the wurtzite structure and ZnS in the zinc blende structure. Agreement between experiment and simulation is found for the 160 °C thermal film with a roughly two monolayer film of ZnO and for oxidation by CHP with a three to four monolayer film of ZnS.     

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.     

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     

Chemical characterization of tribochemical and thermal films generated from neutral and basic ZDDPs using X-ray absorption spectroscopy

X-ray absorption near edge structure (XANES) spectroscopy at the phosphorus L-edge and sulphur L-edge has been used to characterize the chemical nature of tribochemical and thermally generated films from several ZDDP antiwear agents in the neutral and basic forms. Using the P and S L-edge XANES spectra of model compounds with known structure as fingerprints, the chemical structures of P and S species in the films have been identified. P appears in all the films as polyphosphates in different proportions of short and long chain polyphosphates. In some films, polyphosphates are accompanied by unchanged ZDDP. Generally films generated from neutral and basic ZDDPs show similar P and S chemistry (polyphosphates and sulphides) but contain different proportions of unchanged ZDDP. However, the aryl ZDDP films have different polyphosphate structure compared to the alkyl ZDDP films. The sulphur proportion in the tribochemical films is decreased a great deal, but remains in the reduced form. However, S in the thermo-oxidatively generated films, appears both in the reduced and oxidized form, depending on the ZDDP and the temperature.     

The use of X‐ray absorption spectroscopy for monitoring the thickness of antiwear films from ZDDP

X‐ray absorption near edge structure (XANES) spectroscopy at the P K‐edge was used to monitor ZDDP antiwear film thickness with rubbing time. Thermal immersion films of varying thickness were generated from the ZDDP and analysed using XANES spectroscopy and the particle induced X‐ray emission (PIXE) technique. P K‐edge XANES edge jumps and (1s → np) peak heights of the spectra were plotted against PIXE mass thickness values in order to establish calibration curves. Antiwear films were analysed using XANES spectroscopy, and average mass thicknesses were extrapolated from the calibration curves. A set of antiwear films formed in the presence of ZDDP and then further rubbed in base oil (no ZDDP) showed no significant decrease in film thickness. A set of antiwear films rubbed in the presence of ZDDP for various lengths of time showed an increase in film thickness, followed by thinning of the film. The decrease in film thickness is believed to be due to wear caused by the ZDDP solution decomposition products acting as an abrasive in the contact region. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nanoscale chemistry and mechanical properties of tribofilms on Al–Si alloy (A383): interaction of ZDDP,calcium detergent and molybdenum friction modifier

Abstract

The interaction of a friction modifier and a calcium phenate detergent additive, with zinc dialkyl dithiophosphates (ZDDPs) in the formation of antiwear films on A383, has been studied using synchrotron radiation and nanoindentation techniques. X-ray absorption near edge structure (XANES) spectroscopy has shown that films prepared from oils containing both ZDDP and detergent, and ZDDP and molybdenum dithiocarbamate (MoDTC), are chemically similar to, but thicker than those made from oils containing only ZDDP. In addition, wear was greatly reduced in the presence of the detergent which was correlated with the basicity and the presence of the friction modifier. The phosphorus K and L edge XANES spectra show that the tribofilms are polyphosphate glasses of similar nature to those found on steel, but characterised by a shorter chain length. The sulphur K edge shows a MoS₂ like film and under certain conditions, the presence of a sulphate species is detected. High resolution topographic images and mechanical properties were determined by atomic force microscopy and imaging nanoindentation. The films formed in the presence of the detergent exhibited similar mechanical responses independent of the conditions tested. The indentation modulus of the films on the Al matrix always appear much softer than the films formed on the Si grains whether or not the lubricant contains only ZDDP, or both ZDDP and MoDTC.     

Study of the Interaction of ZDDP and Dispersants Using X-ray Absorption Near Edge Structure Spectroscopy—Part 2: Tribochemical Reactions

The antiwear properties of zinc dialkyldithiophosphate (ZDDP), dispersants, and mixtures of ZDDP and different dispersants have been evaluated using a pin-on-flat Plint wear machine. Tribochemical interactions between ZDDP and dispersants have been investigated under boundary lubrication conditions by means of X-ray absorption near edge structure (XANES) spectroscopy, probing the phosphorus, sulfur and nitrogen absorption edges. The results show that the dispersants do not give any wear protection by themselves in the base oil. The dispersants also do not affect the antiwear property of ZDDP under the given testing conditions. The N K-edge XANES analysis indicates that dispersants contribute to the chemical composition of the tribofilms and form mixed ammonium/zinc polyphosphates. Phosphorus in the tribofilms is present mainly in the form of medium-chain polyphosphate on the surface and short-chain polyphosphate in the bulk. Sulfur appears in the tribofilms mainly as sulfide S^-II, possibly zinc sulfide. The presence of dispersants in oil blends does not disturb the polyphosphate (and sulfide) formation, but it does decrease the chain length of the polyphosphate in the tribofilms.     

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.     

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.     

A variable temperature mechanical analysis of ZDDP-derived antiwear films formed on 52100 steel

The nanomechanical properties of antiwear films formed from zinc dialkyl-dithiophosphates (ZDDPs) on steel have been studied by nanoindentation techniques as a function of temperature. X-ray absorption P K- and L- near edge structure (XANES) spectroscopy has shown that films prepared from oils containing ZDDPs on 52100 steel (pin on flat coupons) consist primarily of medium chain polyphosphates with sulphur (S K-edge) predominantly present as sulphide.Using various scanning probe techniques, high-resolution topographic images and mechanical properties can be extracted at the same length scale. Using focused ion beam (FIB) milling we have compared real cross-sectional film thickness with a value estimated from the P K-edge XANES. We report the first measurements of the elastic modulus of the antiwear films at elevated temperatures relevant to the automobile operating conditions (T ≤ 200 °C). The antiwear films demonstrated a relatively constant indentation modulus over a wide range of temperatures consistent with their efficacy in reducing wear by preventing asperity contact.     

The tribological properties and action mechanism of non-active organic molybdate ester and its combination with ZDDP

A non-active molybdate ester (ME) was synthesized in a batch process. Its tribological performance and its synergistic effect with ZDDP in 5CST were evaluated using a four-ball machine, and the chemistry of tribofilms was analyzed with XANES. The results indicate that ME possesses excellent anti-wear and friction-reducing properties, not load-carrying capacity. Both ME and ZDDP show excellent synergistic tribological behavior in 5CST. According to the XANES results, the tribochemical films generated from ME alone are mainly composed of MoO₃, and the tribochemical films generated from the oil blends containing ME and ZDDP consist mainly of MoS₂, sulphate and polyphosphate.