Morphology and Nanomechanical Properties of ZDDP Antiwear Films as a Function of Tribological Contact Time

We have employed scanning force microscopy (SFM) and nanoindentation analysis to track the evolution of tribologically generated antiwear films derived from zinc dialkyldithiophosphate (ZDDP) as a function of rubbing time. The SFM images reveal that film morphology evolves with time through a growth mechanism consisting of three stages. In the first stage nucleation on active sites at the steel surface leads to the growth of distinct segregated islands. In the second stage the islands coalesce causing the film to spread over a larger fraction of the surface. In the final stage continuous rubbing induces the large islands to divide into smaller, densely packed structures. In contrast to the observed morphological changes, rubbing time does not strongly influence the nanomechanical properties of the films. This highlights the importance of film morphology in determining the effectiveness of ZDDP antiwear films. We also observe large variation in both the morphology and nanomechanical properties that are likely due to the heterogeneity in contact pressure at the pin-sample interface of the wear rig.     

The combined effects of ZDDP, surface texture and hardness on the running-in of ferrous metals

The effects of surface characteristics including roughness, lay direction and hardness of rubbing pairs on the antiwear performance of secondary short chain ZDDPs under a boundary lubrication condition are studied experimentally. The antiwear performance of the ZDDPs is evaluated by the duration of running-in periods recorded in wear tests of specially prepared specimens. A running-in period is defined as the time interval from the beginning of a wear test to the time at which the contact resistance between the rubbing pair approaches infinity. The shorter running-in period yields the better antiwear performance. The wear tests were conducted with a reciprocating sliding contact made by flat-on-flat specimens which were made from grey cast iron, quenched medium carbon steel and bearing steel. Two lay directions of the surface texture, namely, parallel and perpendicular to the sliding direction were ground, which made four possible combinations in a rubbing action. The CLA roughness of the specimens ranged from 0.35 μm to 0.04 μm. It is found that to obtain a shorter running-in period and to enhance the antiwear performance of ZDDPs, the following rules should be obeyed. If the hardness numbers of the two rubbing members are near the same, the combination of their lay directions should be both in parallel but perpendicular to the sliding direction and, the roughness values should be smaller than 0.09 μm. If the hardness number of one member is much greater than that of the other, the soft member should be the smaller one and the surface of the hard member should be as smooth as possible. Under any circumstance, the smaller members should be chamfered.     

X-Ray Absorption Study of the Effect of Calcium Sulfonate on Antiwear Film Formation Generated From Neutral and Basic ZDDPs: Part 1—Phosphorus Species

Zinc dialkyldithiophosphates (ZDDPs) from very effective antiwear films in boundary lubrication applications. In most cases, however, the ZDDPs do not work alone. They are formulated with many other additives to provide the performance required by today's modern oils. X-ray absorption near-edge spectroscopy (XANES) has been used to study the antiwear films formed from the commonly used combination of ZDDP and calcium sulfonate in both neutral and basic forms. The results are presented in two papers: Part 1 for the phosphorus species and Part 2 for the sulfur species. XANES showed conclusively that in the presence of LOB (low overbased) or HOB (high overbased) calcium sulfonate under sliding conditions, ZDDPs do not form long-chain polyphosphates that have been associated with antiwear action. Instead, short-chain polyphosphates calcium phosphate are formed. The relative amounts of calcium phosphate formed depend on the ester group of the ZDDP: aryl > n-alkyl > sec-alkyl. Interestingly, this order of ester groups is inversely related to the antiwear effectiveness of the ZDDPs. Thus, it is probable that the addition of either LOB or HOB calcium sulfonate to ZDDP will result in a decrease in antiwear effectiveness of the additive mixture compared to the ZDDP by itself. Wear data support this conclusion. It is suggested that the elimination of long-chain polyphosphates and the formation of calcium phosphates in the tribofilm leads to this decrease in antiwear effectiveness, the latter by abrasion of the antiwear film.     

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 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.     

Film thickness and roughness of ZDDP antiwear films

The two experimental techniques, spacer layer interferometry imaging (SLIM) and atomic force microscopy (AFM), have been used to measure the thickness and roughness of zinc dialkyl dithiophosphate (ZDDP) reaction films formed in a rolling-sliding minitraction machine (MTM) tribometer. The AFM method has been complemented by a novel ZDDP film removal method based on ethylenediaminetetraacetic acid (EDTA) solution. It has been found that the two approaches measure very similar ZDDP film thickness values, lending credence to both methods. However the AFM approach measures much rougher ZDDP reaction films than MTM-SLIM and it is believed that SLIM underestimates the film roughness. Based on this, the use of MTM-SLIM is recommended for monitoring the evolution of antiwear film thickness during rubbing, while AFM should be employed for studying the morphology of antiwear films.     

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.     

Friction and Wear Behavior of Zinc Dialkyldithiophosphate Additive

A method has been developed for monitoring the film-forming properties of antiwear additives in rolling-sliding, lubricated contacts. This makes it possible to study both the kinetics of reaction film growth and also the evolution of the film morphology as a function of rubbing time. The technique has been applied to investigate the behavior of a zinc dialkyl-dithiophosphate (ZDDP) additive solution and to correlate this with simultaneous friction and wear measurements.

The results show that ZDDP forms a thick, solid-like, reaction film in the rubbing tracks, with negligible film growth outside of the track. This film is extremely effective in preventing metal-metal contact. However the film is unevenly-distributed, with its roughness oriented in the direction of sliding. This directional roughness inhibits the entrainment of fluid film in the mixed lubrication regime, increases the proportion of load supported by solid-solid contact and consequently results in the high friction often associated with the use of ZDDP additives.     

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.     

Chemomechanical Properties of Antiwear Films Using X-ray Absorption Microscopy and Nanoindentation Techniques

The first chemomechanical comparison between an antiwear film formed from a solution containing zinc dialkyl-dithiophophates (ZDDPs) to a solution containing ZDDP plus a detergent (ZDDPdet) has been performed. X-ray absorption near-edge structure (XANES) analysis has shown a difference in the type of polyphosphate between each film. The ZDDPdet film has been found to contain short-chain polyphosphates throughout. X-ray photoelectron emission microscopy (X-PEEM) has provided detailed spatially resolved microchemistry of the films. The large pads in the ZDDP antiwear film have long-chain polyphosphates at the surface and shorter-chain polyphosphates are found in the lower lying regions. The spatially resolved chemistry of the ZDDPdet film was found to be short-chain calcium phosphate throughout. Fiducial marks allowed for the re-location of the same areas with an imaging nanoindenter. This allowed the nanoscale mechanical properties, of selected antiwear pads, to be measured on the same length scale. The indentation modulus of the ZDDP antiwear pads were found to be heterogeneous, ~120 GPa at the center and ~90 GPa at the edges. The ZDDPdet antiwear pads were found to be more uniform and have a similar indentation modulus of ~90 GPa. A theory explaining this measured difference, which is based on the probing depths of all techniques used, sheds new insight into the structure and mechanical response of ZDDP antiwear films.     

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.     

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.     

Tribological behaviors and mechanism of sulfur- and phosphorus-free organic molybdate ester with zinc dialkyldithiophosphate

An oil-soluble sulfur- and phosphorus-free organic molybdate ester (ME) was synthesized. The antiwear and friction-reducing properties of ME with zinc dialkyldithiophosphate (ZDDP) in base oils were evaluated by four-ball tester. The results show that ME addition effectively reduced wear scar diameter (WSD) and friction coefficient (μ) as well as good antiwear synergism with ZDDP. The topography, composition and chemical states of typical elements on the worn scar were analyzed by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) and X-ray photoelectron spectrometer (XPS). Smooth and light topography of worn scar further confirms the good antiwear synergism of ME with ZDDP. EDX and XPS analyses indicate that tribo-chemically boundary films formed on the rubbing surface consist of metal oxides, sulfides and phosphates, leading to enhancement of the antiwear and friction-reducing properties of the lubricants, and that the considerable MoS₂ layer especially plays an important role in improving antiwear and friction-reducing properties of oils. The proposed antiwear mechanism involves a synergy between ME and ZDDP.     

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.     

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.     

Antagonistic Interaction of Antiwear Additives and Carbon Black

It is well known that the presence of soot in engine oils can lead to an increase in wear of engine parts. This is a growing problem as soot levels in diesel engine oils are rising due to a combination of extended drain intervals and the various methods employed to reduce NO _x formation such as retarded ignition and exhaust gas recirculation. Several different mechanisms have been proposed by which soot might lead to an increase in wear in mixed lubrication conditions, of which the most widely favoured is abrasion by soot, either of the rubbing metallic parts in engines or of the antiwear additive films formed on rubbing metal surfaces. In this study it is shown that the combination of mixed alkyl ZDDP and carbon black (used as soot surrogate) is strongly antagonistic in terms of wear. In a lubricant containing carbon black, the presence of ZDDP leads to considerably more wear than if ZDDP is left out. A similar, though less severe antagonism is also seen with primary ZDDP and other antiwear and EP additives. By varying the lubricant film thickness it is shown that the effect of carbon black in ZDDP-containing oils is to promote wear up to quite thick hydrodynamic film conditions, approaching the secondary carbon black particle size. It is proposed that the antagonistic wear effect results from a corrosion-abrasive mechanism in which the reaction film formed by antiwear additive and rubbing metal surface is very rapidly and continually abraded by carbon black. At most carbon black concentrations, wear rate then becomes controlled by the rate of initial antiwear additive film formation, which for secondary ZDDP is very rapid, rather than by the kinetics of the abrasive process. From this understanding, strategies for reducing the impact of engine soot on wear can be deduced.     

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.     

Evolution of ZDDP-derived reaction layer morphology with rubbing time

Functional additives, particularly extreme pressure and antiwear additives, in formulated oil will compete to adsorb and function in tribological contacts. A low-polarity commercial base oil, poly-α-olefin (PAO), blended with zinc dialkyl dithiophosphates (ZDDP) has been studied. The tribological performance was evaluated using a ball-on-disk test rig under mixed rolling-sliding conditions in the boundary lubrication regime at 90°C. An adapted in situ interferometry technique was used to monitor the additive-derived reaction layer formation. The thickness of the reaction layer evolves with rubbing until reaching a limiting thickness value of approximately 70 nm. The evolution of the topography and mechanical properties of the ZDDP-derived reaction layer with rubbing time were studied using Atomic Force Microscopy. A constant roughening and hardening of the additive-derived layer with rubbing time is observed and related to the different tribological performance of the layer at different rubbing times.     

Origins of the friction and wear properties of antiwear additives

Experimental techniques have been developed to measure the friction, antiwear film‐forming and wear properties of lubricants in rolling–sliding contact. Friction measurements show that zinc dialkyldithiophosphates (ZDDPs) and also some other phosphorus‐based additives increase friction in mixed lubrication. Film thickness measurements show that this increase in friction correlates with the thickness of antiwear film. They also reveal some of the drivers of antiwear film formation and removal. A novel wear tester is described which enables the mild wear resulting from ZDDP‐containing oils to be monitored. Copyright © 2006 John Wiley & Sons, Ltd.     

Review of the lubrication of metallic surfaces by zinc dialkyl-dithiophosphates

Implementation of tighter environmental restrictions on combustion engine emissions has resulted in the need to create new, more environment friendly engine oil additives. By far the most studied and effective class of antiwear additive are the zinc dialkyl(aryl)-dithiophopshates (ZDDPs). To date, there is no single, effective replacement additive for ZDDP. In order to create an effective replacement, it is first necessary to understand how and why an additive works as well as it does, on all length scales from macro to nano. This comprehensive review of the literature over the last 50 years provides insight into the overall picture of ZDDP by focussing on their chemical characterization, film formation mechanisms, properties and structure with the intent of exposing gaps that still remain in understanding the conundrum of ZDDP.