Effect of the type and concentration of lubricating additives on the antiwear and extreme pressure properties and rolling fatigue life of a four‐ball tribosystem

Tests were performed on two different four‐ball testers. The first was used to determine antiwear (AW) and extreme pressure (EP) properties at sliding friction. The second was used to assess the surface fatigue (pitting) life at rolling movement. Lubricating oils of various chemical compositions were tested. A base mineral oil was blended with two different commercial packages of lubricating additives of AW and EP types. The AW additives contained ZDDP and were blended with the base oil at 0.2 and 3wt %. The EP additives were organic compounds of sulphur and phosphorus, blended with the base oil at 1 and 10wt %. It is shown that AW additives not only improve AW and EP properties but also — at 0.2% — are beneficial for the fatigue life. An increase in the concentration of AW additives leads to an improvement of AW and EP properties but — for one of the packages — reduces the fatigue life. EP additives — at 1% concentration — significantly improve EP properties, and to a lesser extent AW properties. Such a concentration of EP additives has no influence on the fatigue life. An increase in the concentration of EP additives leads to a further improvement of EP and AW properties. However, this is accompanied by a considerable decrease in the fatigue life. By using a scanning electron microscope and energy dispersive spectrometer for analysis of the worn surface, mechanisms of action of various lubricating additives under different friction conditions were identified. Copyright © 2006 John Wiley & Sons, Ltd.     

Tribological Performance and Wear Mechanism of Compound Containing S,P, and B as EP/AW Additives in Copper Foil Oil

Research and development on the high biodegradability of additives is indispensable for environmentally friendly lubricants, which is one of the key factors to advance lubricant technology toward “greener” chemistry. The tribological performance of fatty alcohol polyoxyethylene phosphate acid ester (EK), boron-containing amide (BT), dialkyl dithiophosphate ester (DDE), and a mixture of these (compound) as extreme pressure (EP)/antiwear (AW) additives in hydrogenated base oil (GH) were investigated using a four-ball testing machine. The elemental composition and chemical characteristics of the AW films generated on the surfaces of the steel balls were studied using X-ray photoelectron spectroscopy (XPS), and their AW mechanisms are hereby proposed. Thermal degradation tests were conducted to identify their thermal stabilities using thermogravimetry and differential scanning calorimetry. The results show that these additives can greatly improve the EP/AW properties of GH. XPS analyses of the worn surfaces indicate that decomposed borate esters and organic sulfide or nitrides were adsorbed on the worn surface, and the P and S elements of the compound reacted with the metal and existed in the form of phosphates and sulfates, both of which contributed to the formation of a boundary lubricating film. Moreover, these additives provide the lubricants with excellent oxidation resistance and thermal stability.     

Additive influence on wear and friction performance of environmentally adapted lubricants

In this paper, the influence of concentration level and chemical composition of three different additive types on friction and wear coefficient are presented for a synthetic ester base fluid and a mineral base oil. One extreme-pressure (EP), two antiwear (AW) and two yellow metal passivator (Cu-passivators) additives were used. Factorial experimental design was used as the basis for a systematic evaluation of wear rates under mixed and boundary lubrication conditions. A total of 33 different lubricant blends were tested in a Plint and Partner High Frequency Friction Machine. For the synthetic ester, the extreme-pressure (EP) additive, containing phosphorus and nitrogen, was found to be much more effective in reducing wear than either of the two antiwear (AW) additives tested. In fact, the AW and Cu-passivator additives made little or no contribution to the wear protection in most of the cases studied. A synergy effect between the three additive combinations was observed only for the reference mineral oil blend. A significant difference between the antiwear performance of the test lubricants was found. This study suggests that the traditional “AW” and “EP” labels associated with commonly used additives are poor aids when designing of ester based lubricants.     

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

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

Method for scuffing propagation assessment

This paper describes a method for the determination of scuffing propagation using a four‐ball extreme‐pressure tester. The method has been developed at the authors' laboratory and is a completely new approach to the investigation of scuffing phenomena. A series of lubricants was prepared by blending antiwear (AW) and extreme‐pressure (EP) additives with a mineral base oil. Tribological experiments were then performed using the new method. The aim was to investigate the influence of such additives on scuffing propagation. It is shown that there is a significant influence of AW and EP additives on scuffing. Surface analyses (SEM, EDS) show the decisive role of the chemical reactions of AW and EP additives with the steel surface and their creation of a surface layer whose good antiseizure properties mitigate scuffing propagation and reduce wear intensity. It must be emphasised that the authors consider scuffing to be a process leading to the cessation of the relative movement of a tribosystem, known as seizure.     

EP/AW performance evaluation of some zinc alkyl/dialkyl/alkylaryl‐dithiocarbamates in four‐ball tests

Tribochemistry, the chemistry of interacting surfaces under the influence of a lubricant, helps in the appropriate selection of suitable lubricant additives for specific uses. Modern lubricants are usually formulated from a range of petroleum base oils or synthetic fluids incorporating a variety of chemical additives for performance enhancement. Extreme‐pressure (EP) and anti‐wear (AW) additives are used extensively in lubricants for hypoid gears and metal cutting and forming operations to reduce wear, modify friction, and prevent scuffing of moving metallic parts. The present paper includes the synthesis and the evaluation of the tribological properties of 0.5% (w/v) solutions of some zinc bis‐(alkyl/dialkyl/alkylaryldithiocarbamates) in paraffin oil using 12.7 mm diameter steel bearing ball specimens in four‐ball tests. All the synthesised zinc dithiocarbamate additives in general, and zinc bis‐(morpholinodithio‐carbamate) (A₄) in particular, exhibited good AW, EP, and friction‐reducing properties. Additive A₄ especially gave low values of wear‐scar diameter and coefficient of friction at higher loads and higher values of load wear index and flash temperature parameter during EP tests (ASTM D 2783) and afforded lower values of wear‐scar diameter in a one‐hour wear test (ASTM D 2266–67). The surface topography of the wear‐scar matrix of the used ball specimens was investigated by scanning electron microscopy.     

An ESCA study of the effectiveness of antiwear and extreme‐pressure additives based on substituted phosphorodithioate derivatives,and a comparison with ZDDP

Ashless substituted dithiophosphoric acid derivatives (ADPs) are a new generation of multifunctional additives with promising antiwear (AW) and extreme‐pressure (EP) characteristics. Three such additives synthesised in the authors' laboratory have been evaluated for their AW and EP properties by standard four‐ball friction and wear tests. The friction‐reducing properties of these additives were compared with those of a commercial zinc dialkyldithiophosphate (ZDDP). It was found that the phosphorodithioate compounds studied here possessed excellent AW/EP properties. Their AW characteristics were found to be comparable to those of ZDDP at low loads. However, at higher loads they show inferior AW characteristics in comparison to ZDDP. Nevertheless, ADP derived from cashew nut shell oil had a higher load‐carrying capacity than ZDDP. The mechanism of the AW and EP behaviour exhibited by the different additives was investigated using X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and scanning electron microscopy (SEM) of the worn surfaces formed during friction. XPS and AES analyses of the worn surfaces reveal that the tribochemical film formed on the ADP‐tested surfaces consisted mainly of metal phosphates and only a small amount of metal sulphides, even though the ADPs contained twice the number of sulphur atoms than phosphorus atoms. The ZDDP‐tested surface showed a mixture of metal sulphides and metal phosphates. Alkylamino substitution appeared to have no significant effect on the AW/EP properties of the additive. XPS and AES analyses also revealed that the tribochemical film formed on an ADP‐tested surface was thicker than that present on the ZDDP‐tested surface at low loads, whereas at higher loads the reverse was true. The higher weld load obtained for the blend containing cashew nut shell oil‐derived ADP is attributed to the thicker adsorbed reaction film formed on the surface due to the long alkyl groups present in the original additive structure. Short‐chain alkyl groups, however, form only a thin adsorbed layer, which may get rubbed off during the friction at high load. The low sulphide formation on ADP‐tested surfaces was attributed to the absence of any metal atom in the additive, which would help in the formation of metal sulphides during tribofragmentation and further tribochemical reactions.     

Tribological evaluation of coconut oil as an environment-friendly lubricant

Increased concerns about environmental damage caused by mineral oil based lubricants, has created a growing worldwide trend of promoting vegetable oil as base oil for automobile lubricants. Coconut oil, which is abundantly available in southern states of India, is reportedly being widely used as two-stroke engine lubricant (2T oil) by autorikshaw¹ drivers. A survey among the users of coconut oil as 2T oil brought forth complaints of increased engine wear. This paper presents tribological properties of coconut oil evaluated using a four-ball tester and a test rig to test the wear on two stroke engines. The influence of an antiwear/extreme pressure (AW/EP) additive on the tribological performance of coconut oil was also evaluated experimentally. The addition of the AW/EP additive has brought about considerable reduction in wear with coconut oil as 2T oil.     

Tribological Properties of AW/EP Additives Under Different Thermal Conditions

The authors have investigated the action of compositions containing AW/EP additives under scuffing conditions and the influence of temperature on the wear of friction elements lubricated with selected compositions. It has been stated that postponing of scuffing initiation is not always sufficient to obtain very good strength of the surface layer and decreased wear. Furthermore, the results show the influence of temperature and load on the additive action. Extreme friction conditions result in greater wear intensity and change in the lubricating action of additives.     

The tribological behavior of thiophosphates as additives in rapeseed oil

Two kinds of thiophosphate, tri-n-octyl thiophosphate and tri-n-octyl tetrathiophosphate, were synthesized. The tribological behavior of the synthetic compounds and tricresyl phosphate as additives in rapeseed oil for steel-steel frictional pair was investigated with a four-ball machine. The relationship between the additive structure and tribological properties was explored, while the lubrication mechanisms of the additives were investigated as well. Thus the worn surfaces of the steel ball lubricated with the additive-containing rapeseed oil were analyzed by means of X-ray photoelectron spectrometry and scanning electron microscopy, and the elemental compositions and distributions in the worn steel surfaces were observed and determined with an EPMA-810Q electron probe micro-analyzer. It has been found that the synthetic thiophosphates as additives in rapeseed oil at proper concentrations show better tribological properties than tricresyl phosphate. Tribochemical reactions were involved for steel–steel frictional pair lubricated with the rapeseed oil containing thiophosphates, with the formation of a boundary lubricating and protecting film composed of glyceride of rapeseed oil and tribochemical reaction products of the lubricants. This contributes to improve the tribological properties of the rapeseed oil base stock.     

Enhancing AW/EP property of lubricant oil by adding nano Al/Sn particles

This paper presents results of experiments to enhance antiwear/extreme pressure (AW/EP) properties of a lubricant oil by adding metal nano particles. In this experiment, Al, Sn and Al + Sn nano-particles were selected as trial additives. The AW and EP properties were evaluated on Four-Ball test machine, while the feature and composition of the wear scar surface were investigated by scan electron microscope (SEM) and energy dispersion spectrum (EDS). The test results show that the AW and EP performance can be improved within a wide load range by adding Al + Sn nanoparticles. Analysis of the enhancement mechanism has also been conducted in this experiment and presented in this paper. It is found that nano-Sn particles can be deposited on the friction surface when the pressure was moderate and act as AW additive. It is also found that the nano-Al particles can be deposited under the condition of high load pressure and act as EP additive. Thus, the AW and EP properties of tested lubricant oil have been improved at the same time due to adding both Al and Sn.     

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

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

Tribological behaviour of three phosphate esters containing the benzotriazole group as additives in rapeseed oil

Since the 1970s more attention has been paid to biodegradable lubricants as a way of reducing the pollution caused by lubricants with a mineral oil base. This concern has promoted the use of vegetable oils as alternative base oils. This paper reports on a study of the effect of phosphate esters containing the benzotriazole group as additives in rapeseed oil (RSO), tests being carried out using a standard four‐ball tester. The results show that these additives produce good antiwear performance and load‐carrying capacity compared with RSO alone. Surface analysis of the worn halls was carried out using X‐ray photoelectron spectroscopy. The tribological mechanism is discussed on the basis of the experimental results.     

几种羟基脂肪酸在菜籽油中的润滑行为研究

利用四球摩擦磨损试验机,考察了实验室合成的几种羟基脂肪酸在菜籽油中的减摩抗磨和极压性能。试验结果表明：这些含氧添加剂具有一定的减摩抗磨能力,但对菜籽油的极压性能的没有影响。双羟基脂肪酸比单羟基脂肪酸的减摩抗磨效果更为明显;烷基链较长的羟基甘二酸比羟基十八酸的减摩抗磨性能略好。     

Effects of Chlorinated Paraffin and ZDDP Concentrations on Boundary Lubrication Properties of Mineral and Soybean Oils

Concentration effects of chlorinated paraffin and zinc di-ethylhexyl dithio phosphate on boundary lubrication properties were tested in vegetable and mineral base stocks. Solvent refined low sulfur paraffinic mineral oil (150 N oil) and conventional food grade soybean oil (soy oil) with EP additive concentration of 0–20% (w/w) were used in ASTM D2783 four-ball extreme pressure (4-ball EP) and Twist Compression Tribotests (TCT). Weld points in 4-ball EP and times to failure in TCT at 200 MPa showed that 150 N oil needed more than double treat levels of EP additives to achieve similar boundary lubrication performance as their 5% blends in soy oil. Also, incorporation of 20% soy oil into 150 N oil-based EP additive blends improved the performance to nearly the same level as soy oil only blends of corresponding additives. Boundary lubricity of some soy oil samples was similar to that of a commercial straight oil chlorinated metal forming lubricant. Several suggestions are provided to explain such pronounced influence of the base stock type on EP additive response. The findings suggest that soy oil and other farm-based oils may provide strategies for formulating cost effective industrial fluids and other lubricants.     

Tribological studies on a novel borate ester containing benzothiazol-2-yl and disulfide groups as multifunctional additive

A novel borate ester derivative containing benzothiazol-2-yl and disulfide group (BTSB) was synthesized and characterized. Its tribological properties used as EP and multifunctional additive in rapeseed oil were evaluated using a four-ball tribometer, and its action mechanisms were investigated by the X-ray photoelectron spectroscopy. Results show that the BTSB possesses comprehensive tribological properties in load-carrying, friction-reducing, antiwear, corrosion-inhibiting, and anti-oxidation, which probably has a chance to replace ZDDP partially. Moreover, the decomposed borate esters, organic sulfide and nitrogen adsorbed on worn surface were detected, and S element in BTSB reacted with metal and generated FeSO₄, both of which contributed to the formation of boundary lubricating film.     

2-烷基硫甲基噻吩系列添加剂对菜籽油磨擦学性能的影响

利用四球摩擦磨损试验机考察了噻吩及实验室合成的2－烷基硫甲基噻吩对菜籽油摩擦学性能的影响，用X射线光电子能谱仪（XPS）和扫描电子显微镜（SEM）观察分析了磨损表面的形貌和元素存在状态。用差示扫描量热法（DSC）评价了合成添加剂对菜籽油氧化稳定性的影响，结果表明：2－烷基硫甲基噻吩系列化合物大大提高了菜籽油的承载能力，但加剧了钢－钢摩擦副的磨损。含上述添加剂的菜籽油在摩擦副表面发生摩擦化学反应，生成菜籽油和添加剂共同作用所产生的边界润滑膜，从而改变了菜籽油的润滑性能，2－烷基硫甲基噻吩可明显改善菜籽油的抗氧化性能。     

纳米Al/Sn金属颗粒对润滑油抗磨极压性能的影响

利用四球试验机分别对添加有纳米铅粉、锡粉以及Al Sn金属粉的润滑油进行极压和抗磨性能实验。采用SEM(扫描电子显微镜)对摩擦表面进行观察，采用EDS(能量色散谱仪)对表面进行元素测定。测试结果表明．纳米Al Sn金属粉可在较宽的载荷范围内明显改善润滑油的极压抗磨性能。其作用机理是锡粉在低载荷阶段沉积到摩擦表面起到抗磨剂作用，铝粉在高载荷阶段沉积到摩擦表面起到极压剂作用．从而实现了在低载荷到高载荷范围内对润滑油抗磨极压性能的提高．     

A method for testing lubricants under conditions of scuffing. Part II. The anti-seizure action of lubricating oils

This paper describes an investigation of lubricating oils under extreme-pressure (EP) conditions in a specially modified four-ball tester. A new test method developed at the Tribology Department of ITeE described in Part I of this paper was used. In this, during a test run, the applied load is increased continuously and the friction torque is measured. A sudden increase in the friction torque indicates the collapse of the lubricating film — where scuffing is initiated. The load at this moment is called the scuffing load. If the load is increased further, it is possible to observe scuffing propagation until seizure occurs, i.e., a defined, maximum friction torque is reached. Thus, scuffing is considered as a process leading to seizure. Using the method, tribological experiments were performed employing various lubricating oils consisting of viscosity-index improvers and antiwear (AW) and extreme-pressure (EP) additives added to a base oil. Mineral and synthetic base oils of different kinematic viscosities were used. The aim was to investigate the influence of such lubricants on scuffing initiation and propagation with the present methodology. In Part I it was shown that scuffing initiation depends strongly on the kinematic viscosity of the lubricant; the higher the viscosity, the greater the scuffing load. The presence of AW and EP additives in the lubricant increases the scuffing load significantly. It was also shown that the kinematic viscosity of the lubricant oils has no effect on scuffing propagation. However, scuffing propagation is significantly mitigated by AW and, to a greater extent, by EP additives. The results of surface analyses show the decisive nature of the chemical reactions of AW and EP additives with the steel ball surface under scuffing conditions, as well as the possible diffusion of sulphur and phosphorus. Chemical reactions and diffusion lead to the creation of an inorganic surface layer (probably iron sulphide), the good anti-seizure properties of which limit scuffing propagation.     

Storage stability of sulphurized sperm oil replacements I: Origin and nature of the sludge

Sulphurized sperm oil has been used in numerous lubricant formulations to improve their extreme pressure and antiwear properties. In the beginning of the 1970s, sperm oil became an almost unavailable and expensive raw material. Replacements have been developed, but they are also expensive. Many lubricant manufacturers seem to have turned to sulphurized glycerides, when possible since natural fats and oils are cheaper and more readily available than the synthetic replacements.The greatest limitation on the wider use of sulphurized glycerides in lubricating fluids is their low storage stability in compositions based on paraffinic mineral oils. This has not yet been an object of systematic investigation. The purpose of the experiments presented in the present paper was to examine and suggest the origin and nature of the sludge formed by sulphurized esters of fatty acids in paraffinic mineral oils.The storage stability of sulphurized soya bean oil, lard oil and a mixture of n-butyl and diethylene glycol esters of long-chain fatty acids in three paraffinic base oils was studied. Samples of sludge obtained from the additives after 12 months of storage were characterized.The experimental results confirm earlier observations with model additives that there are less than two sulphur atoms per double bond both in the bulk additive and in the sludge that it forms. The sludge samples were found to have substantially higher acidity than the bulk additives.