Surfactant dithiophosphates lubricating oil additives

Abstract

This paper presents a research on the tribological properties and the action mechanisms of surfactant lubricating oil additives, polyalkoxy glycol ammonium salts and O,O,S-triesters of polyalkoxy glycol dithiophosphoric acid. To understand the physicochemical properties of surfactants, polyalkoxy glycol dithiophosphoric acid behaviour both in solution and at metal surfaces are identified and discussed. The STM adsorption on steel surface, four-ball and ball disc tests of friction of water, synthetic and mineral oil solutions studies of these additives are presented. Friction and wear properties are dependent on tribological parameters, chemical structure of the additives and their surface active behaviour in tribological systems. The relationships are presented on the example of additives with different molecular structures and masses.     

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.     

Lubricating properties of vegetable oils and paraffinic oils with unsaturated fatty acids under high‐contact‐pressure conditions in four‐ball tests

The tribological properties of three kinds of vegetable oils of different composition under high‐contact‐pressure conditions were evaluated in four‐ball tests to elucidate the lubrication mechanism of vegetable oils. The types of fatty acids composing the triglycerides and the concentration of dissolved oxygen appeared mainly to control the lubricating performance. Therefore, glycerol and a paraffinic oil containing fatty acids were tested as a comparison. Further, the influences of fatty acid types, antioxidant additives, and dissolved oxygen in the oils on the lubricating performance were examined. It was shown that linolenic acid with three double bonds was the most effective at higher temperature, where the formation of a friction polymer was observed, although the addition of antioxidant additives suppressed the formation of the friction polymer but reduced the load‐carrying capacity.     

Effect of the structure and metal atom of dialkyldithiophosphate derivatives on the wear behaviour in steel‐zirconia contacts

Wear investigations concerning the different structures and metal atoms of metal dialkyldithiophosphates (MeDTPs) were conducted using a ball‐on‐disc apparatus. Steel ball bearings (3.175 mm in diameter) and counterface discs, made of hot pressed ZrO₂ partially stabilised by Y₂O₃, were used. The synthesised MeDTPs were made up of primary linear aliphatic alcohols with hydrocarbon lengths varying from 8 to 16 carbon atoms, and contained the following metals: zinc(II), iron(III), gallium(III), antimony(III), and copper(II). Tests were performed at room temperature. The sliding speed was set to a constant 0.03 m/s, and a constant 30 N load was used. The additives investigated were used as solutions in n‐hexadecane. The study also focused on the influence of additive concentration on wear. It was found that the effectiveness in reducing wear depends both on the metal atom and on the length of the hydrocarbon chain in the additive's molecules. The lowest wear volumes were observed for additives with n‐octyl and n‐tetradecyl hydrocarbon chains. The worst antiwear performance was observed for n‐dodecyl derivatives. For almost all additives, more concentrated solutions resulted in less wear. Some friction coefficient results are also presented.     

Tribological properties of P‐ and N‐containing organic compounds as potential extreme‐pressure and antiwear additives

An amine salt of an alkoxylphosphate (a P‐ and N‐containing organic compound, PN) was synthesised. Its extreme‐pressure, antiwear, and friction‐reducing properties were evaluated as an additive in liquid paraffin and a mineral oil. Tests were performed on a four‐ball friction and wear tester with an AISI 52100 steel ball self‐mated pair and the results were compared with those of sulphurised olefin (SO), zinc di‐n‐butyldithio‐phosphate (ZDDP), and dibutylphosphite (DBP). The morphologies of the worn steel surfaces were observed using a scanning electron microscope, while the binding energies of some typical elements on the worn surfaces were determined using X‐ray photoelectron spectroscopy. The additives were found to increase the load‐carrying capacity and to reduce wear and friction coefficient considerably. PN as an additive exhibits better load‐carrying, antiwear, and friction‐reducing properties than SO, ZDDP, and DBP under the same test conditions.     

Comparison of boundary lubrication films formed under four‐ball friction test conditions with different AW/EP Additives‐an X‐ray photoelectron spectroscopy study

The antiwear and extreme‐pressure properties of six different types of additive (molybdenum dialkyldithiophosphate, dibenzyl disulphide, molybdenum dialkyldithiocarbamate, zinc dialkyldithiophosphate, chlorinated paraffin wax, and triaryl phosphate) were evaluated by standard four‐ball friction and wear tests. This was followed by scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), and X‐ray photoelectron imaging (XPI) analyses of the worn surfaces to determine the structure of the boundary lubrication film and the mechanism of the tribochemical reaction occurring during the friction process. The presence of the additives in the base oil significantly increased the weld load and drastically reduced the wear‐scar diameter, suggesting antiwear and extreme‐pressure properties of the additives. The enhanced antiwear and loadcarrying capacity of the additive‐containing oils was attributed to the formation of a complex boundary lubrication film formed between the surfaces during the friction process as a result of the tribochemical reaction. The antiwear and extreme‐pressure properties of the additives were explained based on the XPS data. The studies indicated that the lubricating properties of the additives depend on their chemical nature and reactivity with metal surfaces.     

The influence of some additives on the lubricating properties of semi‐synthetic ester oils

This article presents research on the lubricating properties of semi‐synthetic oils, made as compositions of mineral oil and esters. The esters were synthesized from acid substrates from the oxidation of paraffins. The last non‐seizure load (P_n), the weld point (P_z), the load wear index (I_h), and the limiting wear load (G_oz) were measured, and the effects of additives or mixtures of additives were investigated by their effects on these parameters. It was found that the efficiency of the additives depended on their chemical characteristics and concentration, and also on the chemical nature of the ester component of the semi‐synthetic oils.     

Technical note: Extreme‐pressure activity assessment of certain nitrogen and sulphur compounds in lithium‐based grease

In this paper we report on the preparation and extreme‐pressure (EP) activity assessment of certain substituted 1‐amino‐3‐aryl‐2,3‐dihydro‐2‐thioxo‐4,6‐(1H,5H)‐pyrimidinediones as additives in a lithium‐based grease. These additives significantly decreased the wear and friction and possessed the ability to increase load‐carrying capacities and weld loads. Two greases were prepared with the above additives, and both greases exhibited lower values of wear‐scar diameter at higher loads and higher values of weld load in the four‐ball test than the lithium‐based grease alone. The prepared greases also passed rust and corrosion, and oxidation tests.     

Synthesis and tribological behaviour of phosphorus—nitrogen‐modified rape seed oils as biodegradable lubricant additives

Two types of phosphorus—nitrogen‐modified rape seed oils as biodegradable lubricant additives were synthesised and characterised by infrared spectroscopy. Their tribological properties in rape seed oil and in mineral oil were evaluated in a four‐ball tester. The morphologies of the worn surfaces were analysed by scanning electron microscopy. The results show that the modified rape seed oil additives improve the load‐carrying capacity and the antiwear and friction‐reducing properties of rape seed oil more than they do those of mineral oil. The inferred mechanism of lubrication is that a high‐strength adsorption film and/or tribochemical reaction film forms on the rubbing surfaces, due to the carrier effect of long‐chain rape seed oil molecules and to the high reaction activities of phosphorus and nitrogen and their synergism.     

Frictional behaviour of Pb‐Sn thin‐film lubrication

The frictional properties of lead‐tin thin films (thickness of 0.05–0.19 μm) with two types of copper interlayer were investigated. The thin film and the interlayer were formed on a silicon wafer surface by vacuum deposition. Friction tests were carried out using a ball‐on‐disc apparatus in a vacuum chamber. The thin copper interlayer reduced the friction coefficient and prolonged the film life. The effect of load on the friction coefficient is explained by an equation derived using the Hertzian contact area between a sphere and a plate. The thicker copper interlayer did not reduce the friction coefficient but markedly extended the life of the film. In this case, the dependence of the friction coefficient on the load is explained by an equation derived using the Hertzian contact area between a sphere with surface roughness of second order and a plate.     

The temperatures at scuffing and seizure in a four‐ball contact

The temperature of surface asperities affects lubricant‐surface tribochemical interactions. It is important to know the nature of this to identify ways of preventing scuffing and seizure under extreme‐pressure (EP) conditions. A new model for the determination of the temperature of contacting asperities is presented in this paper. It assumes the superposition of thermal processes occurring on the macroscale and thermal phenomena in the contact of asperity tips (microscale). Numerical results have been obtained for conditions of four‐ball testing of various lubricating oils — a mineral base oil with and without antiwear and EP additives. To calculate the scuffing and seizure temperatures, knowledge of the mechanical and physical properties of the test ball material (bearing steel) and lubricants, as well as the parameters describing the surface topography of the balls, was necessary. Friction coefficient curves were also needed; they were determined during four‐ball tests with a continuously increasing load. For the base oil with lubricating additives, the temperature of contacting surface asperities at the moment of scuffing initiation was calculated to be about 230°C and increased to over 1000°C at the highest loading of the four‐ball tribosystem. This suggests the possibility of tribochemical reactions of the lubricating additives with the steel surface, and diffusion of some elements, a modified surface layer having good antiseizure properties being produced. Such a layer prevents seizure of the tribosystem. For the base oil without lubricating additives, scuffing initiated at about 150°C and the temperature exceeded 1200°C at seizure. The temperature values obtained agree with results in the literature.     

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.     

Comparison of the effects of ionic liquid and anti‐wear additives on the tribological properties of Cr―Mo―N coatings

Cr―Mo―N coating was prepared by magnetron sputtering, and its crystallinity and phase structure were analysed by X‐ray diffraction. The tribological properties of the coating separately lubricated with L‐P106 ionic liquid was compared with poly‐alpha‐olefin (PAO) and PAO‐containing MoDTP and ZnDTP additives with a ball‐on‐disc reciprocal friction and wear tester. It was found that the tribological properties of as‐prepared Cr―Mo―N coating vary with varying lubricant systems. Namely, the results indicated that the L‐P106 has better friction‐reducing and wear resistance properties than that of MoDTC and ZnDTP. The analyses indicated that Cr―Mo―N coatings and lubrication films can be considered as a solid–liquid duplex lubricating systems. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthetic aluminium complex grease: A tribological evaluation using a four‐ball test

This paper describes the preparation and performance evaluation of a synthetic aluminium complex grease. The aluminium complex grease was prepared in situ by reacting stearic acid and benzoic acid in the presence of a synthetic base oil, polyalphaolefin. The preparation of the soap (aluminium benzoate stearate hydroxide) was monitored using Fourier transform infrared. Two different extreme‐pressure additives blended with the prepared aluminium complex grease were evaluated for their extreme‐pressure activity in four‐ball and Timken tests. These greases exhibited higher Timken OK loads (60 lb), lower values of wear‐scar diameter at higher loads, and higher values of weld load in the four‐ball test than the aluminium complex grease without additive. The blended greases were also found to pass rust and corrosion, oxidation‐stability, and shear‐stability tests. The topography of the specimens after four‐ball testing was studied with scanning electron microscopy.     

Improvement in the tribological properties of imidazolium‐derived ionic liquids by additive technology

Molecular design of wear‐preventing and friction‐reducing additives for ionic liquids is described. The tribological properties of carboxylic acid‐derived additives were evaluated by a ball‐on‐flat type tribotest under reciprocating motion. Tetraalkylammonium and tetraalkylphosphonium salts of N‐benzyl‐protected aspartic acid were dissolved in 1‐alkyl‐3‐methylimidazolium‐derived ionic liquids. They prevented wear remarkably and reduced friction fairly. Influences of alkyl group in imidazolium molecule on additive response were observed. In tetraalkylammonium‐derived ionic liquids, the additive reduced wear but did not reduce friction under these conditions. The salt of N‐acetyl‐protected glutamic acid prevented wear, but did not reduce friction. Copyright © 2008 John Wiley & Sons, Ltd.     

Tribological performance of sulfonamide derivatives as lubricating oil additives in the diester

The load‐carrying capacity, anti‐wear and friction reduction properties of two sulfonamide derivatives added to a synthetic lubricant (diester) were evaluated using a four‐ball test machine. The results indicate that both additives possess good load‐carrying capacities and excellent anti‐wear and friction reduction properties. The surface topography of the rubbed surface was investigated by scanning electron microscopy, and the chemical nature of the anti‐wear films generated on the steel counter‐face was investigated by X‐ray photoelectron spectroscopy. Surface analysis results show that a stable lubricating film consisting of the reaction layer and adsorption layer was formed on the worn surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Friction and wear behaviour of Sialon/ (Ca,Mg)‐Sialon with lubrication by coated PbS nanoparticles as oil additives

The friction and wear behaviour of Sialon/(Ca,Mg)‐Sialon with lubrication by liquid paraffin containing PbS nano‐particles coated with dialkyldithiophosphate or oleic acid as additives was investigated using an SRV ball‐on‐disc test rig. It was found that the addition of such nanoparticles reduced the friction coefficient of the friction couple irrespective of the concentration of the additive and the wear volume of (Ca,Mg)‐Sialon, especially under relatively high loads such as 150 N or more. X‐ray photoelectron spectroscopy and electron probe microanalysis revealed that a tribochemical film composed of PbSO₄, PbS₂O₃, PbSO₃, etc., was formed on the worn surface, and contributed to the lubricity of the PbS nanoparticles.     

Synthetic polyurea extreme‐pressure greases

This paper describes the preparation of synthetic polyurea greases and evaluates their performance. The polyurea greases were prepared in situ by reacting diisocyanate with monoamines and ethylene diamine in the presence of a synthetic base oil (polyalphaolefin). Two different extreme‐pressure (EP) additives blended with the prepared polyurea greases were evaluated for their EP activity in four‐ball and Timken tests. The additivated greases gave higher loads, and higher values of weld load in the four‐ball test as compared to the polyurea grease without additive. The blended greases were also found to pass rust, corrosion, oxidative stability, and shear stability tests. The topography of the wear‐scar surfaces was investigated using scanning electron microscopy.     

A study of the tribological behaviour of heterocyclic derivatives as additives in rape seed oil and mineral oil

The tribological properties of two novel heterocyclic derivatives as additives in rape seed oil and in mineral oil were investigated using a four‐ball machine. The morphologies and chemical features of the worn steel surfaces were observed and examined by means of X‐ray photoelectron spectroscopy and scanning electron microscopy. Both heterocyclic compounds improved the load‐carrying and extreme‐pressure capacities and the friction‐reducing and antiwear properties of rape seed oil more than they improved those of the mineral oil. Surface analyses of the rubbed surfaces revealed the formation of a protective film containing FeSO₄, organosulphur compound, FeS₂, polymerised ester, and organonitrogen compound when the surfaces were lubricated by rape seed oil containing the additives. The protective film formed during sliding processes contributed to the increase in the wear resistance.     

Effect of the chemical structure of fluorinated esters on the tribological properties of a steel‐on‐steel system

The effect of the chemical structure of fluorinated esters on the friction and wear behaviour of a steel‐on‐steel system was investigated. The friction and wear testing of a steel disc sliding against a counterpart ball of the same steel was carried out using an Optimal SRV oscillating friction and wear tester. The chemical features of the worn steel surfaces were analysed by means of X‐ray photoelectron spectroscopy, and the morphologies and elemental compositions of the worn steel surfaces observed and determined using scanning electron microscopy. The results indicate that a fluorinated ester with methylene groups that are not substituted by fluorine in the acid structure gives the best friction‐reducing behaviour and a keto‐ester shows the best antiwear properties.