Antiwear Behavior of ZDDP and Fluorinated ZDDP in the Presence of Alkylated Diphenyl Amine Antioxidants

Environmental regulations have called for a reduction of phosphorus content in engine oils in recent years. The anti-wear additive zinc dialkyl dithiophosphate (ZDDP), which is also an antioxidant, is one of the most important components of engine oil additives. ZDDP is a major source of phosphorus. One way to reduce phosphorus levels is to replace ZDDP with new environmentally friendly antiwear agents that have similar or superior wear performance compared to ZDDP. Another way to address the environmental issue is to reduce the amount of ZDDP in engine oils. At the same time, it is necessary to increase the efficiency of ZDDP by finding optimum conditions that would result in improved antiwear performance. The antiwear mechanism of ZDDP involves its degradation thermally and tribologically, leading to the formation of an antiwear film that consists of polyphosphates and sulphides. The structure of the antiwear film is almost similar in both types of degradation. But the breakdown efficiency of ZDDP is diminished by the parallel reaction of ZDDP with other additives, as well as the antagonistic effects of these additives. The new fluorinated ZDDP complex developed has shown better wear performance compared to ZDDP. This would allow the possibility of further reduction of phosphorus in engine oils compared to current levels. In this paper we study the interaction of ZDDP and fluorinated ZDDP with alkylated diphenylamine. The impact of antioxidant on wear performance was examined using a ball-on-cylinder tribometer. The interactions between ZDDP and the fluorinated ZDDP with the antioxidant were studied using NMR and the surface of the tribofilm was examined using SEM, TEM, and Auger spectroscopy.     

Additive–additive interaction: an XPS study of the effect of ZDDP on the AW/EP characteristics of molybdenum based additives

The effect of zinc dialkyldithiophosphate (ZDDP) addition on the antiwear (AW) and extreme pressure (EP) properties of molybdenum dialkyldithiocarbamate (MoDTC) and molybdenum dialkyl dithiophosphate (MoDTP) are evaluated by standard Four-Ball friction test and also by the determination of coefficient of friction using an oscillating SRV apparatus. The boundary lubrication film formed on the worn surface using the two molybdenum additives and their combination with ZDDP is investigated by depth profile X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to find out the chemistry of tribochemical reaction occurring at the surface during friction. It is seen that MoDTP possesses better AW properties than MoDTC due to its high reactivity with the metal surface. Nevertheless, the AW characteristics of MoDTC could be improved by the addition of ZDDP. The frictional properties of MoDTP, however, do not change by the addition of ZDDP. The synergistic action of ZDDP on MoDTC is attributed to the enhanced decomposition of MoDTC in presence of ZDDP. This is tentatively explained in terms of some interaction of zinc with the electron donating nitrogen present in MoDTC, which would have helped to increase its tribo-reactivity. XPS studies revealed that in the presence of ZDDP, MoDTC form mainly metal sulphides like MoS₂ and FeS under friction. The MoDTP+ZDDP derived surface, on the other hand, produced mainly metal phosphate along with molybdenum oxysulphides and small amount of MoS₂ and FeS. The mechanism of action of additives is explained.     

环烷酸铋的极压抗磨协同效应研究

探讨了环烷酸铋的合成方法,利用四球试验机评价了环烷酸铋的极压抗磨性能以及与硫化异丁烯(T321)、ZDDP、磷酸三甲酚酯(TCP)、氯化石蜡(T301)、硼酸盐(T361)、MoDDC常用添加剂之间的极压和抗磨协同性能。结果表明,环烷酸铋具有优良的极压抗磨性能,同硫化异丁烯之间有突出的极压协同作用,与ZDDP、MoDDC和氯化石蜡之间也有良好的抗磨协同作用和极压协同作用,可显著提高润滑油的极压性能和改善抗磨性能。     

Copolymeric succinamic acids as antiwear additives: Synergistic and adverse effects

Copolymeric succinamic acid (COSMA) additives have been synthesised in the laboratory and evaluated for their antiwear performance, both alone and in combination with zinc dialkyl‐dithiophosphate (ZDDP) in HVI light neutral oil. COSMA additives show antiwear behaviour and, in combination with ZDDP, exhibit a good synergistic effect, reducing the wear‐scar diameter by 60% and increasing the initial seizure load from 50 kg to 85–95 kg.     

The tribological behaviors of some rare earth complexes as lubricating additives Part 1. An investigation of the friction-reducing behaviors and an XPS study of the tribochemical characteristics

Several rare earth coordination compounds of 8-hydroxyquinoline and of di-n-hexadecyldithiophosphate were synthesized. The burnished films of these coordination compounds on a GCr15 bearing steel (SAE 52100 steel) disc were prepared. The friction-reducing behaviors of the burnished films were evaluated on a DF-PM friction tester. The friction-reducing behaviors of these complexes as additives in a lithium grease were examined on an SRV fretting wear tester. The binding energies of some typical elements in the complexes before and after friction were determined on an X-ray photoelectron spectrometer. It was found that these coordination compounds could form a quite complete burnished film on a GCr15 bearing steel surface. The lowest friction coefficient was obtained with respect to the burnished film of neodymium di-n-hexadecyldithiophosphate (NdDDP), while a decreased friction coefficient was reached with respect to the burnished film of rare earth 8-hydroxyquinolinate, as compared with the non-burnished friction pairs. Besides, the SRV fretting wear test results revealed that NdDDP in lithium grease exhibited better antiwear and extreme pressure properties than zinc di-n-butyldithiophosphate (ZDDP), while the antiwear and extreme pressure performance of rare earth 8-hydroxyquinolinates is comparable to that of ZDDP. The related results will be published in a following part of this work. The XPS results indicated that tribochemical reactions were involved in the wear process of these coordination compounds as lubricants or as lubricating additives. Here in the first part of this work, the friction-reducing behaviors of the burnished films and of the additives in a lithium grease are dealt with, while the XPS study of the tribochemical characteristics of these complexes is also reported.     

Friction and wear of tribofilms formed by zinc dialkyl dithiophosphate antiwear additive in low viscosity engine oils

Friction and wear characteristics of low viscosity SAE 5W-20 engine oils containing different amounts of phosphorus were studied using two different test devices. One was a laboratory high frequency reciprocating rig (HFRR) testing new and used oils at low and elevated temperatures. A direct acting mechanical bucket (DAMB) sliding valvetrain bench test apparatus was used to measure the friction and wear performances of fresh engine oils containing 0, 0.05 and 0.1 wt% phosphorus for a cam lobe rubbing against a tappet insert. The tester was coupled with a radioactive tracer machine (RTM). The results show that in the region of low phosphorus concentration, friction is inversely correlated to temperature. The friction coefficient slightly drops with increasing temperature and increases with increased phosphorus concentration at elevated temperatures. Significant wear is produced at phosphorus concentrations lower than 0.02 wt% at most temperatures. Friction and wear are reduced with the addition of supplemental antiwear additives. MoDTC reduces wear more effectively than ZnDTC in the presence of ZDDP.     

Tribological characteristics of greases with and without metallo-organic friction-modifiers

ABSTRACT

An important focus of grease development is to minimize friction and wear while improving load bearing capacity. ASTM D2266 test method is commonly used to evaluate performance of grease at 75°C, 40?kg and 1200?rpm for 1 hour. However, actual applications may require bearings to be subjected to cyclic loading and variable frequency conditions wherein rotations per minute (rpm), load and duration of test are variables. Five different blends of greases were formulated using ZDDP (3?wt.%), PTFE (2?wt.%), MoDTC (2?wt.%), combination of ZDDP/PTFE in a weight ratio of 3:2 and a combination of ZDDP/PTFE/MoDTC in 3:2:2 weight ratios. They were tested under ASTM D2266 test method as well as under cyclic loading and variable frequency conditions where loads, frequency and duration of the tests were treated as variables. It was found that the combination of ZDDP/PTFE/MoDTC results in significant improvement in the wear and friction under cyclic loading as well as ASTM D2266 test conditions. It was also demonstrated that MoDTC accelerated the tribochemical degradation of ZDDP that resulted in the formation of a protective tribofilm layer on the interacting surfaces. The analysis of the tribofilm formed indicated that when MoDTC was used together with ZDDP and PTFE, a combination of MoS₂, phosphates and sulfates of Zn and Fe are formed whereas when only ZDDP and PTFE was used the tribofilms were largely composed of phosphates and sulfates of Zn and Fe.     

含硫,磷极压抗磨添加剂与CeF3配伍后对摩擦表面反应膜的影响

作者利用Ｘ光光电子能谱（ＸＰＳ）仪和自动划痕试验机研究了锂基脂中ＣｅＦ３与含硫、磷 中剂配伍后对摩擦表面反应膜的影响。划痕试验结果表明，在所试验的六种添加剂中只有二烷基二硫代磷酸锌（ＺＤＤＰ）、磷酸三甲酚酯（ＴＣＰ）和二正丁基亚磷酸酯（ＤＢＰ）与ＣｅＦ３配伍可有效地改善摩擦表面反应膜的附着性。ＸＰＳ研究结果表明，ＺＤＤＰ可改善ＣｅＦ３的成膜能力，抑制ＣｅＦ３的摩擦水解反应。ＣｅＦ３与其它添加剂复合     

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.     

Anti‐wear performance of organomolybdenum compounds as lubricant additives

A four‐ball tester was used to evaluate the anti‐wear performance of three kinds of organomolybdemun compounds in engine oils and lithium soap grease, i.e. molybdenum dialkyldithiophosphate (MoDDP), molybdenum dialkyldithiocarbamate (MoDTC), and sulphur‐ and phosphorus‐free organomolybdeum (molybdate). The results indicate that a low concentration of MoDDP does not improve the anti‐wear properties of the commercial engine oils, but a high concentration of MoDDP can obviously improve the anti‐wear properties of the engine oils. MoDTC does not improve the anti‐wear properties of the engine oils, but worsens the anti‐wear properties of the oils. Significant improvement of the anti‐wear properties is obtained with molybdate added in the four fully formulated oils. Both MoDDP and molybdate have good anti‐wear properties in the lithium soap grease, especially MoDDP with a high concentration. Copyright © 2006 John Wiley & Sons, Ltd.     

Tribological performances of ZDDP and ashless triphenyl phosphorothionate (TPPT) as lubricant additives on Ti–N and Ti–Al–N coated steel surfaces

Abstract

In recent years, there has been much attention on the effects of lubricant additives on the friction and wear properties of surface coatings. However, little research has been conducted to investigate the influence of antiwear additives on the tribological performances of titanium nitride (Ti–N) and titanium aluminium nitride (Ti–Al–N) coatings. It has been reported that introducing aluminium into Ti–N coatings enhanced their oxidation resistance. In this study utilising a pin on cylinder tribometer, lubricants containing zinc dialkyl dithiophosphate (ZDDP) or a more environmentally friendly alternative, ashless triphenyl phosphorothionate (TPPT), were used. Experimental results revealed that ZDDP and TPPT helped to reduce wear on both coatings through the formation of a tribofilm, although it was also found that both additives increased the friction coefficient on both surfaces. Based on overall findings, this paper suggests the use of TPPT as a suitable ZDDP replacement for providing wear protection on Ti–N and Ti–Al–N coatings.     

一种耐轴承腐蚀和磨损的复合锂基润滑脂的研制

研究不同类型极压抗磨剂、抗氧剂和防锈剂等对复合锂基润滑脂性能的影响,并复配一种多功能复合添加剂制备出复合锂基润滑脂。所研制复合锂基润滑脂的梯姆肯值为266 N、高温下氧化诱导期为761 min、滴点大于330℃,且通过了FE 8轴承磨损和EMCOR轴承腐蚀台架的检测。研究结果表明:所研制的复合锂基脂具有优异的极压抗磨、高温抗氧及耐轴承腐蚀和磨损等性能,应用效果良好。     

A study on tribological behaviours of ZDDP in polymer thickened lubricating greases

Zinc Dialkyl Dithiophosphate (ZDDP) is a well‐known multifunctional additive for soap based lubricating greases. Polymers are being studied for their performance as lubricating grease thickeners and rheology modifiers. In this work the tribological study of ZDDP was carried out in polypropylene (PP), maleated polypropylene (mPP) and linear low density polyethylene (PE) thickened lubricating greases. Performance of lithium grease was taken as a reference. The tribological properties were evaluated using a four ball tester for EP properties and Optimol SRV‐III machine for coefficient of friction. The mechanism of action of ZDDP in polymer greases was established through analysis of the worn surface of steel balls with scanning electron microscope (SEM) and energy dispersive x‐ray spectroscopy (EDAX). The results show that the performance of ZDDP depends on the thickener system. The antiwear and EP property exhibited by ZDDP varies from polymer to polymer. Poor performance was observed with PP type thickener whereas performance in PE and lithium grease was comparable. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Topography and nanomechanical properties of tribochemical films derived from zinc dialkyl and diaryl dithiophosphates

In this paper we present recent results from an on‐going effort to characterize the nanomechanical properties of a variety of tribochemical, antiwear films through the use of modern scanning probe techniques. The two types of antiwear wear films studied, derived from zinc dialkyl dithiophosphate (alkyl ZDDP) and zinc diaryl dithiophosphate (aryl ZDDP), were chosen because they possess significantly different wear characteristics. High resolution AFM topographic images showed significant differences between the two types of films. More interestingly, high resolution imaging and quantitative mechanical properties testing using the interfacial force microscope (IFM), revealed different elastic and plastic properties between the two types of films; in addition each type of film possessed several distinct regions with respect to mechanical properties. The maximum values for elastic modulus and hardness were located on the highly loaded regions of the alkyl ZDDP films which exhibited the best tribological performance. In contrast, the aryl ZDDP films, which exhibited poorer antiwear behaviour, were devoid of such resilient regions. Our results correlate the macroscopic wear behavior of the tribochemical films to differences in the mechanical properties on a nanometer scale. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tribological behavior and nature of tribofilms generated from fluorinated ZDDP in comparison to ZDDP under extreme pressure conditions—Part 1: Structure and chemistry of tribofilms

Tribofilms generated under boundary conditions at extreme pressure using lubricants containing fluorinated zinc dialkyl dithiophosphate (F-ZDDP) and zinc dialkyl dithiophosphates (ZDDP) were examined. F-ZDDP demonstrated superior wear performance compared to ZDDP even at lower phosphorus levels. The tribofilms generated by ZDDP and fluorinated ZDDP were analyzed using scanning electron microscopy, Auger electron spectroscopy and XPS. Transmission electron microscopy was conducted on wear debris. XANES spectroscopy was used to study the chemical and bonding environment of sulfur and phosphorus in these tribofilms. A phenomenological model of the tribofilms generated by ZDDP and fluorinated ZDDP was developed based on the experimental results.     

Boundary lubrication mechanisms of carbon coatings by MoDTC and ZDDP additives

Fuel economy and reduction of harmful elements in lubricants are becoming important issues in the automotive industry. An approach to respond to these requirements is the potential use of low friction coatings in engine components exposed to boundary lubrication conditions. Diamond-like-carbon (DLC) coatings present a wide range of tribological behavior, including friction coefficients in ultra-high vacuum below 0.02. The engine oil environment which provides similar favourable air free conditions might lead to such low friction levels.In this work, the friction and wear properties of DLC coatings in boundary lubrication conditions have been investigated as a function of the hydrogen content in the carbon coating. Their interaction with ZDDP which is the exclusive antiwear agent in most automotive lubrication blends and friction-modifier additive MoDTC has been studied. Hydrogenated DLC coatings can be better lubricated in the presence of the friction-modifier additive MoDTC through the formation of MoS₂ solid lubricant material than can non-hydrogenated DLC. In contrast, the antiwear additive ZDDP does not significantly affect the wear behavior of DLC coatings. The good tribological performances of the DLC coatings suggest that they can contribute to reduce friction and wear in the engine, and so permit the significant decrease of additive concentration.     

The Effect of FeS Solid Lubricant on the Tribological Properties of Bearing Steel under Grease Lubrication

In order to improve the tribological properties of 52100 steel under grease lubrication, FeS solid lubricant was used in two ways. Low-temperature ion-sulfurization technology was utilized to prepare solid lubricant iron sulfide (FeS) films on the surface of 52100 steel, and FeS particles were mixed into the lithium grease as additive. The friction and wear properties were examined systematically on a “ball-on-disc” testing machine. The results showed that the tribological properties of bearing steel under grease lubrication can be improved either by using ion-sulfurization technique or by adding FeS microparticles into the grease. The tribological performance of sulfurized surface lubricated by grease is better than that of a plain surface lubricated by grease containing FeS microparticles at lower load and speed. The plain surface lubricated by the grease containing FeS micropaticles possesses better antiwear property under harsher conditions. The mechanism of the experimental results is discussed in detail.     

Film Formation of Non-Phosphorus Wear Inhibitors

The time-dependent film formation of two potential non-phosphorus supplemental wear inhibitors in the presence of secondary zinc dialkyldithiophosphate (ZnDTP) was studied by electrical contact resistance (ECR), auger, and X-ray photoelectron (XPS) spectroscopy. One weight percent of a molybdenum dithiocarbamate or an ashless dithiocarbamate was blended with a secondary ZnDTP, sufficient in quantity to yield 0.05 wt% phosphorus at blend level. A thorough surface examination by auger and XPS, coupled with the ECR results, detailed the deleterious effects that these supplemental antiwear additives had on ZnDTP antiwear film formation. Both carbamates interfered with antiwear film formation by secondary ZnDTP. It is speculated that MoDTC generated a competing molybdenum sulfide film that oxidized over time to form MoO ₃ , which promotes wear in the ECR bench test based on literature insight. Ashless DTC also formed a competing antiwear film but not as good a film as from ZnDTP alone.     

Spurious Mild Wear Measurement Using White Light Interference Microscopy in the Presence of Antiwear Films

Commercial scanning white light interference microscopes are able to map surface topography to very high resolution and can thus measure very small amounts of wear on rubbed surfaces. These instruments are therefore being increasingly used to study aspects of mild wear. It is shown in this Technical Note that, when used on surfaces that have been rubbed in lubricants containing the antiwear additive zinc dialkyldithiophosphate (ZDDP), some white light interference microscopes can produce an apparent but spurious wear measurement. The transparent and relatively thick antiwear film generated by ZDDP on rubbed surfaces produces an optical path difference that is incorrectly interpreted as wear. It is thus suggested that surfaces that have been rubbed in lubricants containing ZDDP or other thick film-forming additives should be treated to remove tribofilms prior to wear measurement using scanning interference microscopy.