Molecular Design of Environmentally Adapted Lubricants: Antiwear Additives Derived from Natural Amino Acids

Novel environmentally adapted lubricant additives were synthesized from cystine (Cys ₂ ), an essential amino acid obtained from natural sources. The structural feature of cystine is a dimeric amino acid with a central disulfide bond. The carboxyl groups in Cys ₂ were converted to corresponding esters by reaction with long-chain alcohols. The resultant diesters were soluble in poly-alpha-olefin (PAO) and ester-type synthetic oils. The structural features of the new additives include multifunctional groups on the same molecule, such as disulfide as a tribologically active moiety and polar functional groups as anchors to friction surfaces. The additives consist of hydrogen, carbon, nitrogen, oxygen, and sulfur; they are free of phosphorus, chlorine, and metals. The tribological properties of the additives in a solution of synthetic oil were evaluated by performing laboratory tribotests under boundary conditions. The Cys ₂ -derived additives exhibited comparable antiwear properties to the conventional additive zinc dialkyldithiophosphate (ZnDTP). The additives showed good antiwear properties even at low concentrations of sulfur (160 ppm) in synthetic hydrocarbons such as PAOs. A high concentration of sulfur (640 ppm) was required to obtain an optimized antiwear performance of the synthetic esters as a base oil. The new additives reduced the friction coefficient of PAOs and synthetic esters. A saturated ester of Cys ₂ reduced the friction of PAOs and synthetic esters up to oil temperatures of 150°C. The lubrication mechanism was discussed with respect to the role of functional groups in the additive molecule. The use of amino acids as versatile building blocks for the synthesis of environmentally adapted additives was also pointed out.     

Effective viscosity of oils containing VI improver and its relation to wear

The effective viscosity of oils containing polymethacrylate and olefin copolymer additives has been determined using the electrical resistance technique in a rolling, four-ball machine. The effective viscosity is affected mainly by type, concentration and molecular weight of the polymer additive. The experimental results indicate that the thickening effect, following addition of a polymer, is decreased significantly in terms of film thickness, after frictional contact. The results of sliding wear tests correlate well with calculations of effective viscosity indicating that only the viscosity at high shear rates (> 10⁶s⁻¹) is responsible for the wear preventing property of these additives. No antiwear properties, in terms of boundary lubrication, are observed     

Oil-Soluble Fluorinated Compounds as Antiwear and Antifriction Additives

Many studies have been published on the use of solid fluorinated compounds as lubricants and lubricant additives, but much less has been done with oil-soluble fluorinated additives.

This paper describes a study of fluorinated telomers, especially fatty acids and their amine salts, for boundary lubrication (antiwear conditions). The antiwear effectiveness of these fluorinated compounds is compared with a commercial additive, zinc di-n-butyl dithiophosphate (ZDTP).

Modern analytical tools are used to study surface layers (XPS, automatic wetting balance), and wear particles (IR) to determine their antiwear mechanism. Special attention is given to fluorinated reaction film formation.     

Antiwear Additives for Ester Oils

Esters for lubrication can be classified into two major groups. One is the neopentyl type or the so‐called hindered type. The other is the triglyceride type, which includes vegetable oils. The improvement of the antiwear properties of carboxylic esters by additive technology under boundary lubrication conditions is studied in this paper. Two strategies are considered, based on the structure of the esters. Triglyceride‐type esters are mainly used as rapidly biodegradable fluids. They have carbon‐carbon unsaturated bonds in their molecules, which are susceptible to auto‐oxidation, and this auto‐oxidation has deleterious effects on the antiwear properties. A synergistic effect of antioxidants and antiwear additives on wear reduction was observed. The mechanism is discussed and practical solutions proposed. Neopentyl‐type esters have thermal and oxidative stability. For these oils, the antiwear properties depend on the polarity of the additive and base oil. The effect of molecular structure on the antiwear properties is discussed. Computer simulation is used to understand the mechanism of action. Examples of molecular design of antiwear additives for neopentyl‐type esters are also proposed.     

Perfluoropolyalkylether lubricants under boundary conditions: Iron catalysis of lubricant degradation

Perfluoropolyalkylether (PFPAE) oils and oil-based greases exhibit signifcant degradation under boundary lubrication conditions. In the absence of significant concentrations of oxygen, as in the case of spacecraft orbital environments, the degradation mechanism consists of two steps: (1) the initial reaction of the PFPAE molecules with freshly exposed iron to form the Lewis acid, FeF₃, followed by (2) the reaction of the FeF₃ with unreacted PFPAE molecules, which results in the cleavage of the etherate linkages. The result is an autocatalytic degradation that takes place at temperatures below the onset of thermal decomposition. This mechanistic hypothesis is supported by the following experimental results: (1) The reaction of PFPAE with FeF₃ has been shown to give rise to fluorinated-ketone and acid fluoride ether-cleavage products that are more reactive than the parent PFPAE molecules and have lower molecular weights and thus poorer lubricating ability. (2) FeF_x compounds are formed in the wear tracks of wear-test components under boundary lubrication conditions. On the basis of these experimental results, poor performance can be predicted for PFPAE oils under conditions in which high temperatures (approximately 350 °C) and freshly exposed metal surfaces are present (i.e., the conditions of boundary lubrication). This prediction is corroborated through wear tests in which the performance of PFPAE is compared to the performance of commercial petroleum-based and synthetic- hydrocarbon lubricants to which lead naphthenate or antimony dialkyldithiocarbamate have been added. The test results confirm the well-known fact that the antiwear additives are very important to prolonged wear life under boundary lubrication conditions. In addition, the results show that, compared to the other lubricants tested, the PFPAE lubricants do not demonstrate adequate lubrication pevormance. Both the PFPAE degradation mechanism and the fact that soluble antiwear additives are not currently available imply that PFPAE lubricants are not currently suitable for applications in which boundary lubrication conditions exist, especially when high loads are involved.     

Investigation of anti-wear additives for low viscous synthetic esters: Hydroxyalkyl phosphonates

Various synthetic esters are widely applied as lubricating fluid to reduce friction and wear at tribological contact. Among them low viscous synthetic esters are expected to improve fuel efficiency by minimizing the fluid friction. These low viscous esters are composed of short-chain fatty acids. Therefore, low viscous synthetic esters are inherently polar molecules. Since efficiency of anti-wear additives decreases with increase of polarity of the base oil, new additive technology is requested.In this work, hydroxyalkyl phosphates [P(O)(OCHRCH₂OH)₃], and hydroxyalkyl phosphonates [P(OH)_n(OCHRCH₂OH)_3−n, where n=1,2] are proposed as novel anti-wear additives for polar synthetic esters. The anti-wear additives are evaluated under the boundary conditions. The additives prevent wear in polar esters, in which conventional anti-wear additives do not work at all. Interestingly, effects of substituent in additive molecule on anti-wear properties are found. Alkyl and aryl derivatives reduce wear remarkably, whereas allyl derivatives exhibit poor results. It is speculated that the anti-wear inefiiciency of allylic compounds is due to auto-oxidation of the additives.A facile preparative method for hydroxyalkyl derivatives characterizes the present additive system. They are prepared in situ by simply mixing phosphonic acid and substituted epoxides. Flexiblity of lubricant design can be made possible by the present additive system.     

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.     

Tribological properties of 2 novel Mo/B–based lubricant additives in polyalphaolefin

Two kinds of Mo/B oleic diethanolamide derivatives (coded as YXM and YXB) were synthesised, and their tribological properties were evaluated using a 4‐ball machine. Results indicate that the 2 novel additives show excellent antiwear and extreme pressure properties. When 2.5 wt% YXM was added into the base oil, the wear scar diameter was reduced by 42.2%, and the P _B value was increased by 170.4%; when 2.5 wt% YXB was added into the base oil, the wear scar diameter was reduced by 23.1%, and the P _B value was increased by 167.1%. The worn surfaces of the lubricated GCr15 steel were analysed by using scanning electron microscopy and X‐ray photoelectron spectroscopy. It is indicated that the variation of tribofilm species produced by a chemical reaction between the additives and the steel surface plays an important role in inhibiting wear and friction. A model was used to analyse the action mechanism. According to the analysis, the tribofilm is composed of an adsorption layer and a reaction layer, and it could effectively protect the steel surfaces from direct contact.     

A reciprocating wear test for evaluating boundary lubrication

A reciprocating wear tester was used to investigated the nature of antiwear boundary lubrication films formed by several ZDDP additives in mineral oil. Under the test conditions examined in this work, antiwear films are relatively thick (approximately 0.1 μm), and so can be readily detected by optical microscopy. Film formation occurs after only a few centimetres of sliding on smooth hard surfaces, whereupon wear essentialy ceases. On rough surfaces, film formation does not take place until the surfaces have run-in, whereupon wear again ceases. Antiwear films did not form on steel pins softer than Rc 25, which wore by an oxidative mechanism. The extent of run-in or rough surfaces before film formation can be used as a measure of the effectiveness of an antiwear additive. Antiwear films are resistant to wear, so once formed they can provide sustained wear protection in base oil. However, antiwear films can be removed by wear in the presence of hydroperoxides, or by running against a new rough countersurface.     

Micellar calcium borate as an antiwear additive

The mechanisms of action of a new generation of antiwear additives is studied here by means of energy‐filtering transmission electron microscopy (EFTEM) carried out on the wear particles generated during friction tests between two ferrous surfaces (under boundary lubrication conditions). This paper deals with the structural and physico‐chemical changes that colloidal particles, calcium carbonate (CC) and calcium borate (CB) overbased salicylates detergents, have undergone during the build‐up of the interfacial antiwear tribofilm. EFTEM allowed us to investigate the nature of wear fragments originating from the film, stemming from CC and CB micelles, and to make a comparison regarding the tribofilm formation mechanisms. It appears that the CC wear debris are mainly crystalline and contain a high concentration of iron (as abrasive iron oxide Fe₂O₃), limiting their antiwear action. Consequently, CC micelles do not lead to an effective protective tribofilm. On the other hand, CB micelles do have an antiwear action, which we explained by the formation of a glassy iron borate tribofilm during the friction tests. Many of the CB wear fragments are composed of this amorphous material containing very small crystallites of residual calcite. Boron (contained in the CB micelles) is responsible for the presence of amorphous zones of the film and acts as a glass former, in a comparable way to phosphorus in zinc dithiophosphate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Lubricity characteristics of ethyl hexyl esters of mono‐, Di‐, and triethenoic acids

Ethyl hexyl esters of oleic, linoleic, and linolenic acids were synthesised and thermally polymerised to obtain products with viscosities in the range of hydrocarbon lubricants at 100°C (11–22 cSt). Molecular weight, elemental analysis, IR, ¹³C NMR, and intrinsic viscosity data showed that most of these derivatives are mixtures of monomers, dimers, and trimers and have linear and cyclic products with predominantly trans characteristics. The lubricity characteristics were determined on a friction and wear tester under conditions of thick‐film lubrication. A comparison was made with hydrocracked hydrocarbon lubricants of comparable viscosities at 100°C and comparable viscosity indices. It is inferred that all the esters maintained relatively thicker surface films and much lower friction coefficients than the hydrocarbon oils. The wear‐scar data show that the antiwear characteristics of polymerised ethyl hexyl oleate and linoleate are only slightly inferior to those of the hydrocarbon oils, but at higher temperatures their antiwear characteristics rapidly deteriorate while the friction coefficients markedly increase and become comparable to those of hydrocarbon oils. These studies are being undertaken with a view to selecting and modifying vegetable oils containing mixtures of fatty acids for obtaining esters of outstanding friction, wear, and film‐forming characteristics.     

The Effect of Morphology on the Tribological Properties of MoS<Subscript>2</Subscript> in Liquid Paraffin

The tribological properties of liquid paraffin (LP) containing molybdenum disulfide (MoS₂) additives, including nano-balls, nano-slices, and bulk 2H-MoS₂, are evaluated using a four-ball tribometer. Results show that all MoS₂ additives used can improve the tribological properties of LP, and that nanosized MoS₂ particles function as lubrication additives in LP better than micro-MoS₂ particles do. The LP with nano-balls presents the best antifriction and antiwear properties at the MoS₂ content of 1.5 wt%. This is ascribed to the chemical stability of the layer-closed spherical structure of nano-balls. The Stribeck curves confirm that the rotation speed of 1,450 rpm used is located at the mixed lubrication region under 300 N. MoS₂ nano-slices have small sizes and easily enter into the interface of the friction pair with a roughness of 0.032 μm, functioning as a lubricant in LP better than nano-balls do at the MoS₂ content of 1.0 wt%. The Stribeck curves also show that the differences between the two nano samples were magnified at high rotation speeds in hydrodynamic lubrication region. The application of nano-slices in high sliding speeds will be more advantageous. This work furthers the understanding of the relationship between the tribological properties and morphology of MoS₂.     

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.     

Antiwear Properties of Phosphorous-Containing Compounds in Vegetable Oils

Antiwear properties of vegetable oils were investigated under boundary lubrication conditions using the four-ball wear test (ADTM D 4172). Additive-free vegetable oils exhibit similar antiwear properties, which are superior to those of additive-free mineral oils. Phosphorus-containing compounds such as zinc bis(dialkyldithiophosphate) and dialkyl phosphonates improve the antiwear properties of vegetable oils. The effect of the additives on wear reduction was found to depend on the peroxide value of the base oil. It is considered that peroxides decompose the antiwear additives to less active forms. The formation of peroxides by the autooxidation of vegetable oils was observed even at room temperature. Sunflower oil exhibits good oxidation stability, which may promise success in various applications.     

Antiwear,Antifriction, and Extreme Pressure Properties of Motor Bike Engine Oil Dispersed with Molybdenum Disulfide Nanoparticles

This work presents studies on the antiwear, antifriction, and extreme pressure properties of motor oil dispersed with MoS₂ nanoparticles. Commercial oil (SAE 20W-40 grade) is dispersed with stabilized MoS₂ nanoparticles in 0.25, 0.5, 0.75, and 1 wt%. The test oils are tested for antiwear, antifriction, and extreme pressure properties on a four-ball wear tester. The wear and friction offered by nanolubricants has decreased remarkably compared to the commercial base oil. The weld load and load wear index of oils dispersed with nanoparticles were improved substantially compared to the commercial base oil. Metallographic studies conducted on the wear balls from the extreme pressure test show that nanoparticles are deposited on the worn area along with additives in the oil, thereby preventing welding of the surfaces. An optimum weight fraction is arrived at for best performance. A synergy between the additives in the oil and dispersed nanoparticles has been observed, resulting in less dispersion for best results. It is found that beyond an optimum weight percentage of nanoparticles, the trends tend to reverse, resulting in greater wear and friction.     

Antagonistic Interaction of Antiwear Additives and Carbon Black

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

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.     

Antiwear Tribofilm Formation on Steel Surfaces Lubricated With Gear Oil Containing Borate,Phosphorus, and Sulfur Additives

The formation of antiwear tribofilms plays a critical role in the longevity of automotive gears. The focus of this experimental study was on the lubrication efficacy of gear oils with different contents of borate-, phosphorus-, and sulfur-containing additives leading to the formation of protective tribofilms. Experiments were performed with AISI 52100 steel balls sliding against AISI 52100 steel disks in baths of different oils at ambient (～32 °C) and elevated (～100 °C) temperatures under load and speed conditions favoring sliding in the boundary lubrication regime. Friction coefficient responses accompanied by electrical contact voltage measurements provided real-time information about the formation and durability of the antiwear tribofilms. The wear resistance of the tribochemical films was quantified by wear rate data obtained from surface profilometry measurements of wear tracks on the disk specimens and sliding tests performed at ambient temperatures after the formation of the tribofilms during elevated-temperature sliding. Results indicate a strong dependence of tribofilm formation on temperature and type of additives. The slightly lower friction and higher wear resistance obtained at elevated temperatures with blended oils is attributed to the increased chemical reactivity of additives containing borate, phosphorus, and sulfur, leading to the formation of durable tribofilms. Relatively higher wear resistance and faster tribofilm formation were obtained with the borate-enriched gear oil formulations.     

Influence of temperature and ZDDP concentration on tribochemistry of surface-capped molybdenum sulfide nanoparticles studied by XANES spectroscopy

The tribological behavior of surface-capped MoS₃ nanoparticles (nano-MoS₃) in hydrocarbon oils was studied in combination with ZDDP at test temperatures in the range of 100–160 °C and at ZDDP content of 0–1.0 wt% in oil. It was demonstrated that this combination of additives demonstrates high antiwear and antifriction efficiency, especially at high temperatures and low ZDDP content. X-ray Absorption Near Edge Structure (XANES) spectroscopy at the sulfur, molybdenum, and phosphorus edges was used to identify the chemical species in the tribochemical films. It was established that the tribofilms formed by combination of ZDDP and nano-MoS₃ contain phosphate-based layers incorporating MoS₂-type fragments. An increase in temperature and ZDDP content results in an increase in tribofilm thickness, while the relative Mo content in tribofilm decreases. Under the tested conditions, the best tribological properties are demonstrated by the composition comprising 500 ppm Mo and 0.1 wt% ZDDP in oil.     

Tribological Properties of Muscovite/La2O3 Composite Powders as Lubricant Additives

Muscovite/La₂O₃ composite powders were prepared by ball-milling solid-state chemical reaction at room temperature. The phase composition and micromorphology of the composite powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). The tribological properties of different samples were tested and compared using four-ball wear testing on an MMW-1A multifunctional friction and wear testing machine. The SEM micrography and energy spectrum of the composite powders illustrated that La₂O₃ particles were coated on the surface of muscovite particles. The results of the friction tests indicated that lubrication oil with muscovite/La₂O₃ composite powders presents better friction reducing and antiwear properties than that of the base oil, and the friction coefficients and diameters of wear scars decreased by 47.6 and 11.2% using 500SN base oil with 0.6g/L of muscovite/La₂O₃ composite powders as additives, respectively. The composite powders with 5 wt% La₂O₃ present the best comprehensive tribological properties. The micromorphology and chemical composition of the worn surface were analyzed by SEM and EDX, which confirm that the composite powders directly participate in the complicated physicochemical process of reactions on the worn surfaces, therefore improving the tribological properties of the base oil.