Decomposition Of ZDDP Research Articles

Synergistic and antagonistic interaction between ZDDP and TiO2 nanoparticles under boundary lubrication

Lubricants are complex mixtures of additives that serve multiple purposes, and these additives must work synergistically at best and at worst, not interfere with each other. In previous research, nanoparticles of TiO2 have demonstrated excellent tribological outcomes when used singularly as an additive in lubricants. In this study, we have shown that when nanoparticles of TiO2 and ZDDP are used together they act antagonistically by resulting in very high wear rates wherein nanoparticles of TiO2 remove the protective tribofilms from ZDDP as they form on the surface. To further investigate this behavior, we used these additives in alternating sequential order and introduced them at different time points (15 & 30 min) during the one-hour testing. Very synergistic interaction is seen when TiO2 is used first followed by ZDDP wherein the TiO2 reacts with the Fe substrate to form FeTiO3. This layer then serves as a superior surface for Zn-polyphosphates and Ti-phospate tribofilms formed due to the decomposition of ZDDP under tribological conditions. On the other hand, when use of ZDDP is followed by TiO2 we see outcomes that favor the shorter duration of use of ZDDP, however, results are not as effective as former case where TiO2 is followed by ZDDP. The addition of TiO2 earlier in the tribological process assists in the development of more robust complex polyphosphate tribofilms leading to much desirable tribological properties.

Low and high temperature effects on friction and wear performance of Cr-plated cylinder liner

Cr-plated cylinder liners with good wear and corrosion resistance as well as high strength are suitable for application in low-carbon fuel engines. A reciprocating friction and wear tester was used to measure the friction and wear performance of the Mo-sprayed piston ring and Cr-plated cylinder liner at low and high temperatures. For the low temperature conditions from −20 °C to 20 °C, the worn surface of tribo-pair was more prone to spalling. Once the load went up to 66 MPa under low temperatures, cylinder liner scuffing occurred. As the temperature increased from 90 °C to 240 °C, the honing textures of the Cr-plated cylinder liner presented gradually shallow with more abrasive marks along the sliding direction. The tribo-chemical reaction products of zinc dialkyldithiophosphates (ZDDP) with white bright spots distribution provided better protection of the tribo-pair to avoid severe fatigue spalling. The influence of temperature effects on the ZDDP decomposition and surface spalling damage should not be underestimated for Cr-plated cylinder liners.

Adsorption and decomposition of ZDDP on lightweight metallic substrates: Ab initio and experimental insights

Lightweight alloys substitute steel in a wide range of industrial applications. It is still unclear whether the lubricant additives currently employed to reduce friction of sliding metallic parts are also efficient on non-ferrous substrates. In particular, the functionality of zinc dialkyldithiophosphates (ZDDPs) in contact with Al- and Mg-containing alloys still needs to be understood. In this work, we describe the properties of ZDDP at Al(111), Al(001), Al(331), Mg(0001) and Mg17Al12 surfaces and interfaces. Our calculations indicate that molecular fragments originated from ZDDP chemisorb more strongly on the intermetallic phase Mg17Al12 with respect to aluminum and magnesium, due to the higher surface energy of the mixed substrate. Ab initio molecular dynamics simulations show that the kinetics of the additive decomposition is significantly different on Al and the mixed phase. These results are supported by atomic force microscopy sliding tests, which revealed that the tribofilm formation is observed only on the latter substrate. This work suggests that the tribological performance of lightweight alloys can be enhanced by increasing the additive-surface chemical interactions.

Boundary lubrication performance of polymeric and organic friction modifiers in the presence of an anti-wear additive

The effect of oleic acid, oleyl alcohol and oleyl amine based organic friction modifiers (OFM), ester and ethoxylated fatty ester based di-block polymeric friction modifiers (PFM) and Zinc dialkyldithiophosphate (ZDDP) on the boundary lubrication of steel surfaces was studied using a ball-on-disc tribometer equipped with optical interferometry. Frictional performance of oil blends containing the OFM/PFM, with and without ZDDP, was investigated at a slide roll ratio (SRR) of 100% and 130 °C for a rubbing duration of 24 h. Surface topography measurements using 3D surface profilometer and scanning electron microscopy (SEM) were used to quantify the anti-wear performance. Comparison of optical interferograms and friction data showed that formation of a thicker tribofilm does not always translate to effective friction reduction. Our experiments showed that PFMs generally provide better friction reduction than OFMs with or without ZDDP by effectively eliminating the boundary regime. This was attributed to the ability of PFMs to form a tenacious low shear strength film on the metal surface due to its polymeric nature. In contrast, both the friction modifiers had a negative effect on the anti-wear performance of ZDDP. The observed tribological response is attributed to either preferential adsorption of the friction modifier over ZDDP or ZDDP decomposition products. This notion was further corroborated by results obtained from energy-dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS) with depth profile analysis, which showed lower concentration of ZDDP derived products for the formulation containing both the friction modifier and ZDDP.

Effect of temperature on tribological performance of organic friction modifier and anti-wear additive: Insights from friction, surface (ToF-SIMS and EDX) and wear analysis

Tribological performance of an organic friction modifier (glycerol monooleate – GMO), an anti-wear additive (zinc dialkyldithiophosphate – ZDDP) and its combination was studied using a ball-on-disc tribometer equipped with optical interferometry at 90 °C and 140 °C. Higher temperatures were needed for the formation of additive layers and chemically reactive anti-wear protective layers. Comparison of Stribeck curves obtained after different rubbing durations showed that GMO reduced friction at low speed sliding-rolling contact. Despite notable decrease in the base oil viscosity with increase in temperature — in turn, increasing the severity of asperity contact — GMO exhibited enhanced frictional performance. The presence of ZDDP alone in the formulation led to significant increase in friction at both low and high temperatures, with the thickness of tribofilm unaffected after prolonged rubbing. The addition of friction modifier to ZDDP-based formulation reduced the friction in the boundary lubrication regime where longer rubbing aided in effective friction reduction at higher temperature. For the binary additive system, the friction coefficient was found to lie between the values corresponding to the single additives. The observed tribological response is attributed to preferential adsorption of the friction modifier over ZDDP and/or ZDDP decomposition products. This notion was corroborated by the results obtained from static and dynamic time-of-flight secondary ion mass spectrometry (ToF-SIMS) and energy-dispersive X-ray spectroscopy (EDX) analysis of the disc surface post tribological measurement. The concentration gradient of different chemical species detected in the tribofilm correlated with the frictional performance of the additives. Analysis of surface roughness and wear scar width showed an improvement in wear performance at higher temperature suggesting the friction modifier and anti-wear additive adsorbed on the surface providing a mechanical barrier. A synergistic effect on the wear performance was observed for GMO + ZDDP-based formulations, which resulted in a smaller wear scar compared to the individual additives.

On the Transient Decomposition and Reaction Kinetics of Zinc Dialkyldithiophosphate.

Despite the ubiquitous use of the zinc dialkyldithiophosphate (ZDDP) as an antiwear additive, no complete information is yet available on its exact decomposition reactions and kinetics to form triboreactive protective films on contacting surfaces. This hinders the replacement of ZDDP with more environmentally friendly additives of similar antiwear capabilities. Using a multitechnique approach, this study shows that before the formation of a phosphate-rich protective film, the decomposition of ZDDP proceeds by forming intermediate zinc sulfide and sulfate species, which can be mechanically mixed with the iron oxides on the rubbing steel surfaces. The mixed sulfur-oxide layer can play different vital roles including binding the subsequently formed phosphate layers with the metal surface. These layers consist mainly of zinc thiophosphate of initially short chains, which are formed due to the excess concentration of metal oxide on the surface. As the concentration of the oxide decreases in the subsequent layers, the short chains start to polymerize into longer ones. The polymerization process follows first-order reaction kinetics with two distinctive phases. The first one is a fast transient burst phase near the steel surface, whereas the second phase dominates the formation process of the layers away from the substrate and is characterized by slow kinetics. The findings of this study provide new insights into the decomposition mechanisms of the currently most widely used antiwear additive and open future opportunities to find green alternatives with similar superior antiwear properties.

Computational studies on the effects of substituents on the structure and property of zinc dialkyldithiophosphates

The substituent effect on the structure and property of zinc dialkyldithiophosphates (ZDDPs) have been investigated by DFT calculations. More than ten kinds of substituents including alkyl and aryl groups were chosen for assembling more than twenty ZDDPs. The structural features, thermal decomposition of ZDDP and the hydrolysis of alkaline tetranuclear zinc molecules with various alkyl and aryl substituents have been examined. It is found that the substituents have almost no effect on their central structures, but have significant effect on the thermal decomposition of alkyl- and aryl-substituted ZDDPs and their dimers. The calculations on the hydrolysis of tetranuclear ZDDPs suggest that the reaction free energies are affected by the substituents and the hydrolysis temperature. The radical species derived from ZDDP decomposition tends to be adsorbed on metal surface via multi-coordination manner.

Tribological properties of Mg/Al–CO3 layered double hydroxide as additive in base oil

The tribological performance of Mg/Al–CO3–layered double hydroxide (LDHs) nanoparticles in base oil was studied as a sole additive and in combination with zinc dialkyldithiophosphate (ZDDP) at 100°C. Results show that LDHs could improve antifriction and antiwear properties of base oil. The blend with LDHs alone shows better antifriction properties than that of the mixture of LDHs and ZDDP, but the addition of ZDDP helps to stabilise the friction coefficient. Surface analyses have been performed to study the morphology, nanoparticle distribution and chemical species in the tribofilm. The results show that tribofilms contain Mg, Al, C, O, Zn, P and S, and the structure of Mg/Al–CO3–LDHs changes under shearing stress and this process can help reduce friction coefficient. Thus, LDHs could be chemically incorporated into tribofilm to reduce the polyphosphate chain length originated from ZDDP decomposition resulting in a medium chain polyphosphate, which provides very good wear protection.

Optimization of Extreme Load and Break-in Period in Plain ZDDP Oil with FeF3 Catalyst Using Design of Experiment and Fundamental Study under Different Speeds

The mechanism of tribofilm formation and breakdown was carefully followed and studied in 0.1 P% (percentage phosphorus content) plain zinc dialkyldithiophosphate (ZDDP) oil in the presence of iron fluoride (FeF3) catalyst under extreme Hertzian contact pressure (3.0 GPa) and two different rotational speeds or variable speed with break in period (100 rpm for the first 5,000 revolutions and a 700 rpm until failure or 100,000 revolutions, whichever comes first). At the onset of large frictional fluctuations, the contact surface temperature increased significantly and reached 90°C ± 5°C. The present article describes an innovative method of reducing the surface temperature by using a break in period of 2 or 3 min and rerunning the test until failure. The two different rotational speeds or variable speed will be compared to a steady-state speed of 700 rpm.Thermal decomposition of ZDDP is examined in the presence of powder and dispersed FeF3 using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Surface analyses were carried out using scanning electron microscopy (SEM) coupled with X-ray of the wear tracks, transmission electron microscopy (TEM), and auger electron spectroscopy (AES). Results showed that submicrometer dispersed FeF3 provided excellent wear protection when combined with ZDDP in the variable-speed test with break-in by forming a tribofilm that is amorphous in nature and rich in phosphorus, which was shown by the TEM and X-ray analyses.

Enhanced DLC wear performance by the presence of lubricant additives

Lubricant additives play significant role for reducing friction and wear of mechanical elements. The additives presented in 5W30 oil were developed for metal surfaces. However, they have been used in engine pieces covered with DLC coatings because they also offer the potential to reduce friction losses and wear in automotive applications. The friction and wear tests were carried out by using a UMT-CETR ball-on-disk tribometer in rotational mode under 5W30 synthetic oil at 100 °C. The X-ray photoelectron spectroscopy (XPS) showed the presence of Mo and S in the wear tracks. These elements are from decomposition of ZDDP and MoDTC additives producing MoS2 in DLC surface, which offers enhanced durability by low wear rate.

Smart materials behavior in phosphates: Role of hydroxyl groups and relevance to antiwear films

The elastic properties of materials under high pressure are relevant to the understanding and performance of many systems of current interest, for example, in geology and tribology. Of particular interest is the origin of the dramatic increase in modulus with increasing pressure, a response which is also called "smart materials behavior." In this context, simple phosphate-containing materials have been studied experimentally and theoretically, and the origins of this behavior have been associated with factors such as coordination of the cations and changes in the degree of polymerization and hydrogenation of the phosphate units. In the present paper we extend the former analysis on simple metal phosphate model compounds to so-called thermal films, an intermediate stage in the formation of effective antiwear films. The material was produced by heating a commercial zinc dialkyldithiophosphate (ZDDP), a common antiwear additive in lubricating oils, in poly-alpha-olefin base oil solutions to 150 degrees C, a process known to produce the thermal films. Its structure and equation of state were studied by means of x-ray diffraction and IR synchrotron radiation techniques during compression up to 25 GPa in a diamond anvil cell as well as during the subsequent decompression. As is the case for the simple metal phosphates, we find that the thermal films are relatively soft at low pressures but stiffen rapidly and ultimately amorphize irreversibly at high pressure. However, in addition to phase transformations involving cation sites occurring in the metal phosphates studied previously, thermal films undergo displacive transitions associated with instabilities of the hydroxyl groups. These results may imply that ZDDP ligands and those of the transformed materials not only affect ZDDP decomposition rate in engines but also the mechanical properties of the resulting antiwear films.

The chemical characterization of tribofilms using XANES — Interaction of nanosize calcium-containing detergents with zinc dialkyldithiophosphate

A Plint friction and wear tester was used to investigate the effect of several calcium-containing detergents on the tribological and tribochemical performance of a zinc dialkyldithiophosphate (ZDDP) lubricating oil additive in a low-sulfur base stock, 100N. Thus, the friction and wear behavior of a steel-on-steel contact lubricated by 100N oil containing ZDDP alone and ZDDP–detergent mixtures at 100 °C was evaluated in a pin-on-disc configuration. The wear scar width of the upper steel pins was determined using an optical microscope, while the tribofilms formed on the lower steel discs were analyzed using X-ray absorption near edge structure (XANES) spectroscopy and X-ray photoelectron spectroscopy (XPS). At the same time, the thermal-oxidation films of the oil blends containing different additives were also prepared on the same steel discs and analyzed using XANES spectroscopy for comparative studies. It was found that in simple formulations the three kinds of calcium-containing detergents improved the friction-reducing and antiwear abilities of the 100N base stock. This was related to the individual tribochemical reactions and the deposition (in one case) of nanosized CaCO3 on the rubbing steel surface, indicating that the calcium-containing detergent had a synergistic antiwear performance with the ZDDP tested in the present work. Moreover, the calcium-containing detergents contributed to retarding the thermo-oxidation and friction-induced decomposition of ZDDP in 100N oil and influenced the composition and thickness of the tribofilms, which could be dependent on the molecular structures of the detergents and directly related to the tribochemistry of ZDDPs in mineral oil. The rubbing of the steel–steel pair at 100 °C was more beneficial for the deposition of nanosized calcium carbonate on the steel surface than heating at 150 °C. The calcium-containing detergents alone in the base stock also experienced tribochemical reactions, leading to obvious changes in the oxidation state of S in the corresponding tribofilms. Therefore, it was supposed that the tribochemical reactions of the ZDDP and detergents together with the deposition of nanosized CaCO3 on the rubbing steel surfaces accounted for the good antiwear performance of the blended oils.Key words: ZDDP, detergent, thermal film, tribofilm, tribochemistry, XANES, XPS.

ZDDP and MoDTC interactions in boundary lubrication—The effect of temperature and ZDDP/MoDTC ratio

Tribofilms formed under boundary lubrication from ZDDP and MoDTC additives alone or in different ratios in the lubricant have been studied. The tribological performance is linked to the tribofilm properties and consequently to the lubricating conditions. Tribofilms are formed using a reciprocating pin-on-plate tribometer. Surface sensitive analytical techniques, such as energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) have been used for tribofilm characterisation. The XPS peaks have been deconvoluted to characterise the species formed in the wear scar. The formation of species with different tribological properties, due to the decomposition of ZDDP and MoDTC molecules as a result of testing temperature, is shown. Surface analyses have shown that MoDTC decomposes, even in low-lubricant bulk temperature tests (30 °C), forming the same species as in high-lubricant bulk temperature tests (100 and 150 °C) but the tribofilms give different tribological performance. The effectiveness in friction reduction is shown to depend on the ratio between what are defined as high- and low-friction species in the tribofilm.

Thermal degradation behavior of zinc dialkyldithiophosphate in presence of catalyst and detergents in neutral oil

Thermal decomposition of zinc dialkyldithiophosphate (ZDDP) is examined in presence of a noble catalyst iron fluoride (FeF3), using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The influence of heating rate, isothermal holding period and catalyst concentration was verified. The role of FeF3 on ZDDP decomposition mechanism was analyzed using 31P-NMR. This study also focused on the effect of FeF3 on ZDDP decomposition in combination with detergents (Ca-sulfonate, Mg-sulfonate and Cophenates). The decomposition temperature of ZDDP is reduced significantly in presence of FeF3. Thanks to FeF3, the ZDDP decomposition temperature is lower even in the presence of the detergents, while the detergents greatly retard the ZDDP decomposition. The 31P-NMR studies confirmed a faster decomposition and a different decomposition mechanism of ZDDP in presence of FeF3

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.

Tribochemical Conversions of Zinc Dialkyldithiophosphate (ZDDP) Under Extremely Different Pressure Conditions

The authors performed ball-on-disk and four-ball tests. The former gave much less severe conditions than the latter. A ZDDP-containing package, blended with a mineral base oil, was tested. Completely different mechanisms of ZDDP conversions were observed. During ball-on-disk tests, ZDDP undergoes partial tribochemical decomposition. It results in a modification of the surface of test specimens—organic compounds are produced and zinc atoms diffuse into the surface. During four-ball tests, advanced structural decomposition of ZDDP takes place—S and P take part in tribochemical reactions. Probably inorganic compounds are produced, whereas there is a lack of a layer of organic ones adsorbed on the surface. The generation of inorganic compounds results from chemical reactions of decomposed ZDDP with the surface of steel specimens as well as diffusion of some elements (e.g. S) into the surface. Good antiseizure properties of such inorganic structures help to improve the tribological characteristics under severe test conditions.

Morphological evolution of films formed from thermooxidative decomposition of ZDDP

Zinc dialkydithiophosphate (ZDDP) materials are important antiwear/antioxidant additives in most modern lubrication formulations. The current understanding of the formation of antiwear films from ZDDP involves a tribochemical and thermooxidative component. We examine here the changes in the topography and structure of films formed by the thermooxidative decomposition of ZDDP in base oil. We probe the evolution in topography with scanning force microscopy (SFM) as a function of oil heating time and observe changes on both a mesoscopic and sub-micron scale. These morphological changes are compared with infrared spectra to correlate the chemical composition of thermal films to their topography.

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.

Application of soft X-ray absorption spectroscopy in chemical characterization of antiwear films generated by ZDDP Part I: the effects of physical parameters

X-ray absorption near edge structure (XANES) spectroscopy has been used to study the chemical nature of the antiwear films generated on steel surfaces using zinc dialkyldithiophosphates (ZDDPs). The spectra were recorded using total electron yield (TEY) and fluorescence yield (FY) to investigate the chemical nature of P, S, Ca, O and Fe on the surface and in the bulk, respectively. In the first part of this study, the effects of physical parameters on the composition and mechanism of antiwear film formation is discussed. It has been found that lower concentration of ZDDP, higher temperature and higher load all increase the rate of ZDDP decomposition; and longer rubbing time, higher concentration of ZDDP, moderate temperature, higher load and smooth surfaces help to form long chain polyphosphates. The sulphur in the film in most of the cases is in the reduced form. The presence of sulphate in very short rubbing times or high temperatures has also been detected. When the spectra from the TEY mode and FY mode were compared, a layered structure was found in most of the films. In these films, there is a longer chain polyphosphate on the topmost surface and a shorter chain polyphosphate in the bulk. At short rubbing times and low temperature, unchanged ZDDP is also present in the film. Depth profiling using X-ray photoelectron spectroscopy showed that the antiwear film formed in 30 min is thinner compared with a 12 hour film. Based on the above information, a new mechanism for antiwear film formation is proposed.

The theory of antiwear for ZDDP at elevated temperature in boundary lubrication condition

Abstract Based on the experimental results from mechanical and physical analyses, this paper proposes a theory of antiwear for ZDDP added to a base oil at elevated temperature in boundary lubrication condition. It is assumed that the decomposition products of ZDDP can react chemically with one or both of the rubbed surfaces. The theory is established with physical and mechanical models, instead of considering the process of the formation of chemical film. In the theory, a simplified elastic model is employed to predict the duration of run-in and the critical thickness of a chemical film that should grow to achieve the antiwear performance. In this model the hardness and roughness of the contacting surfaces are the most important characteristics which control whether or not an antiwear film can be developed or the amount of wear under rubbing action. Once a chemical film is established, the growth of the film is predicted with a diffusion model. The amount of the chemical film which is scraped off the rubbed surface can also be determined theoretically with this model. The theory also takes into account the effect of decomposition of ZDDP on the growth of chemical film. In accordance with the experimental data in hand, the theory is confirmed to be correct.