Oxidative degradation of synthetic ester and its influence on tribological behavior

The oxidative degradation process and oxidation mechanism of di-2-ethylhexyl sebacate (DEHS) were studied in present work. GC–MS results revealed that 2-ethyl-1-hexanol and mono (2-ethylhexyl) sebacate were major degradation products in the liquid phase. Further investigation of degradation mechanism of DEHS showed that oxidation reactions and hydrolysis were main factors degradation of DEHS. The four-ball test results showed that chemical composition changes of DEHS during oxidation could significantly influence its tribological behavior. The formation of hydroperoxides in the initial oxidation period could seriously deteriorate lubrication properties of DEHS. However, as the oxidation proceeded, high polar products (acids, alcohols and monoesters) formed could significantly improve the anti-wear and friction-reducing properties of DEHS.     

Study of zinc dialkyldithiophosphate in di-ethylhexyl sebacate using electrochemical techniques

Electrochemical techniques have been applied to detect the redox behaviour of the antiwear additive zinc dithiophosphate (ZDDP) in di-ethylhexyl sebacate (DEHS) base fluid solution and to study the interaction of ZDDP with ferrous surfaces. Using cyclic voltammetry it has been shown that the ZDDP is oxidised in a chemically-irreversible process at applied potentials above 1.2 V vs. Pt with an iron electrode. The influence of applied electrode potential on friction and wear characteristics of ZDDP in DEHS has also been investigated. Reciprocating rubbing tests have shown that ZDDP is effective in reducing wear only under oxidising conditions. This electrochemical approach can be used to explore the operating conditions and mechanism of action of antiwear additives.     

Tribochemistry of n‐hexadecane in different material systems

Hexadecane is widely used as the model base oil to investigate both tribological effectiveness and tribochemical reaction mechanisms of various antiwear and extreme pressure additives. On the other hand, it is well known from existing references that hexadecane, similarly to hydrocarbon oils, oxidizes during the lubrication process of tribological systems. It has frequently been pointed out that carboxylic acids are formed which — reacting with rubbing surfaces — generate soaps. Most recent studies, however, demonstrate that the oxidation process under friction conditions is very complex and the major oxidation compounds from hexadecane under boundary friction conditions relate to other oxygenates than carboxylic acids. This paper aims to examine what types of surface compound are generated from the hexadecane lubricant in the friction contact zone. Tribological tests were performed on a ball‐on‐disc tribometer. The discs used were made from several materials (steel, aluminium, brass, bronze). Fourier transform infrared (FTIR) microspectrophotometry and techniques involving a scanning electron microscope equipped with an energy‐dispersive spectrometer were used to analyse tribochemical reaction products formed on different substrates. Analytical results obtained clearly demonstrate a similar tribochemical reaction process operating on all the metals tested. The FTIR results obtained allowed new absorption bands to be discovered and accounted for. These absorption bands have been assigned to specific complex compounds. Copyright © 2006 John Wiley & Sons, Ltd.     

X‐ray absorption near‐edge structure analysis of tribofilms generated by highly efficient,friction‐reducing additive in water–polyglycol–glycol lubricant

The development of environment‐friendly lubricant additives can make a valuable contribution to addressing human health and energy problems. In the present work, the compound ammonium tetrathiomolybdate was synthesised and used as a highly efficient, friction‐reducing additive in water–polyglycol–glycol lubricants. Its tribological properties were tested by a four‐ball machine, and the composition of the tribofilm was identified by X‐ray absorption near‐edge structure (XANES) spectroscopy. The tribological test results indicated that the additive cannot only reduce the friction coefficient value, but can also shorten the rubbing time needed to produce a ‘stable friction coefficient value’. The XANES results showed that the tribofilm is mainly composed of an adsorbed layer and a tribochemical layer; the formation of sulphate and molybdenum trioxide in the tribofilm on the metal wear surface is responsible for the excellent anti‐friction performances of the additive. Copyright © 2009 John Wiley & Sons, Ltd.     

Tribochemical reaction of hydrogenated diamond-like carbon films: a clue to understand the environmental dependence

Tribological behavior of hydrogenated diamond-like carbon (DLC) films and Si incorporated DLC (Si-DLC) films deposited on Si (100) wafer by r.f.-plasma assisted chemical vapor deposition were investigated by ball-on-disk type tribometry in various environments. The friction tests were performed in ambient air of relative humidity ranging from 0% to 90% or dry oxygen environment. We focused on the tribochemical reactions by analyzing chemical composition, chemical bond structure and agglomerated shape of the debris. High and unstable friction behavior was observed in both humid air and dry oxygen environments. In these environments, Auger spectrum analysis showed that the debris contained large amounts of Fe. Significant incorporation of Fe in the debris resulted from the wear of the steel ball, which might be enhanced by the surface oxidation of the ball. These results show that the humidity dependence of friction coefficient is not an inherent tribological property of DLC films but results from the surface reaction of the steel ball in humid environments. Two possible reasons for the Fe rich debris affecting the friction behavior are presented. Reduced dependence of the friction coefficient on the relative humidity observed for Si-DLC films is discussed in terms of the two possible reasons.     

Friction‐reducing and antioxidant capabilities of engine oil additive systems under oxidative conditions. II. Understanding ligand exchange in a molybdenum dialkyldithiocarbamate/zinc dialkyldithiophosphate additive system in various base oils

The ligand‐exchange reactions between molybdenum dialkyldithiocarbamate, Mo(dtc)₂, and zinc dialkyldithiophosphate, Zn(dtp)₂, have been investigated during inhibited oxidation in a model hydrocarbon (hexadecane) and in a series of Group I–IV base oils at 160°C. These investigations revealed that the ligand exchange leads to formation of single‐exchange products, Mo(dtc)(dtp) and Zn(dtp)(dtc), and double‐exchange products, Mo(dtp)₂ and Zn(dtc)₂, and that the extent of the exchange is significantly affected by oxidation and inhibition reactions involving the original additives, the ligand‐exchange products, the base oil, and base oil‐derived oxidation products. It is concluded that there are two reaction sequences that control the product distribution and additive consumption during oxidation in different base oils. The first sequence involves the formation of peroxy radicals and hydroperoxides, and the decomposition of hydroperoxides by Zn(dtp)₂ and Zn(dtp)(dtc). One of the most important factors affecting this sequence is the base oil oxidisability. The second sequence involves inhibition of oxidation by peroxy radical‐trapping antioxidants naturally present in or added to the oil, or formed during the oxidation. Zn(dtc)₂ and Zn(dtp)(dtc) appear to be very effective in this respect and are, therefore, preferentially consumed. This preferential consumption shifts the ligand‐exchange equilibrium towards the formation of Mo(dtc)(dtp) and Mo(dtp)₂. The combined effect of the two sequences depends on base oil properties. The first sequence predominates in base oils exhibiting high oxidisability (e.g., in Group I oils) and the second in paraffinic oils, such as Group III and IV oils, having low oxidisability and no sulphur or aromatics. the retention of friction‐reducing capability with the Mo(dtc)₂/Zn(dtp)₂ additive system during oxidation appears to be tied to the first sequence, which leads to consumption of Zn (dtp)₂, since the friction‐reducing capability ceases when Zn (dtp)2 is consumed and hydroperoxides can accumulate in the system. Consequently, the best retention of friction‐reducing capability is achieved in bases oils with low oxidisability.     

The Effects of Magnetic Treatment on the Tribological Behavior of AISI 1045 Steel under Lubricated Conditions

The mechanical and tribological properties of pulse-magnetized and untreated AISI 1045 steel were studied comparatively. The microhardness and microstructures of treated and untreated steel samples were analyzed to evaluate magnetic treatment effects on the mechanical properties. Dislocation densities were calculated from X-ray diffraction data according to the Williamson-Hall method. Tribological tests were conducted using a ball-on-disk reciprocating friction and wear tester. Scanning electron and energy-dispersive microscopies were used to analyze the morphologies and elements of worn surfaces. Dislocation densities of AISI 1045 steel were found to increase by 16.5% after magnetic treatment. Treated steel performed better under polyalphaolefin (PAO) base oil lubrication with each of five additives, especially when oleic acid was 0.2 and 1.5% (by mass), and the wear scar width and friction coefficient of treated samples were 46.9 and 16.4% lower than those of the untreated samples, respectively. Morphological analyses indicated that micromagnetic fields generated during friction tests not only promoted oxidation of the worn surface and debris but also produced thinner tribofilms that included chemical and adsorbed films.     

Tribological studies of thin diamond-like films synthesized using high-speed plasma jet

In this paper, the tribological studies of diamond-like films under slip friction conditions are described. The films have been deposited from various materials (steel, aluminum, copper, and others). These films are deposited by the chemical vapor deposition method using a supersonic high-temperature plasma jet generated by a high-enthalpy plasmatron with a sectionalized interelectrode insert and a cold gas curtain for the walls of the discharge chamber. Tribological studies of the deposited films are performed using the friction simulator in the disc–ring system at rotational reverse motion. As a lubricant, 2% carboxymethylcellulose solution is used. Considerable differences in the tribological behavior depending on the substrate material, where the film has been deposited, are noted.     

Tribological Performance and Transfer Behavior of Lubricating Oils at Head-Disk Interface under Volatile Organic Contamination

Tribological performance of head-disk interface (HDI) under volatile organic contamination was investigated using a contact start/stop (CSS) tester. Slider and disk surfaces were analyzed using Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) after CSS tests. The CSS test results indicated that the friction forces were high and unstable under contamination. Transfer of lubricating oil onto the slider surface was detected after the CSS tests. The transfer amount of lubricating oil was revealed to be dependent on the chemical structure of the terminal group in the lubricating oil. Piperonyl (–CH₂−phe=(O)₂=CH₂) terminated AM3001 lubricating oil was lost more easily than two hydroxyl (–OH) terminated Tetraol lubricating oil, probably because of the weak attractive force of the piperonyl groups with carbon overcoat. TOF-SIMS chemical images indicated that the transferring behavior of the lubricating oil onto the slider surface during CSS tests was dependent on the chemical structure of volatile organic contaminants. The lubricating oil became built up on the slider surface when the dioctyl sebacate (DOS) pollutant used. In contrast, the lubricating oil distribution on the slider surface was uniform under a polydimethylsiloxane (PDMS) vapor. The different transfer behavior of lubricating oil onto the slider surface may be resulted from the changeable surface properties of slider and disk because of the coexistence with gaseous contaminants.     

Effect of mechanical shear on the thin‐film properties of base oil‐polymer mixtures

The thickness and frictional characteristics of thin lubricant films are known to affect the fuel economy properties of oils. The base oil and polymer compositions of the lubricant are generally considered to be critical chemical factors that can influence these thin‐film lubricant properties in new oils. However, it is important to produce lubricants with good fuel economy properties that are maintained after the lubricant is degraded. Lubricants in use can undergo oxidation and mechanical shear degradation. The effect of oxidation degradation on thin‐film physical properties has previously been studied. This paper investigates the effect of mechanical shearing on thin‐film properties. Dispersant olefin copolymers are found to reduce thin‐film friction in simple mixtures and in fully formulated oils. In simple mixtures, shearing the dispersant olefin copolymers does not affect the friction‐reducing ability of these polymers. In fully formulated oils, even though shearing diminishes to a degree the friction‐reducing ability of dispersant olefin copolymers, these copolymers can still provide significant friction reduction.     

Tribological properties and lubrication mechanisms of a Ag–Mo composite

A composite material containing silver and molybdenum metals was fabricated by powder metallurgy method with a Ag/Mo molar ratio of 2 : 1 and the sintering temperature is 700°C. Tribological properties, especially the solid lubrication behaviours during oxidation of the composite in air, were considered from room temperature to 600°C. Phase composition, microstructure and thermal behaviour of the composite were analysed before and after tests to investigate the lubrication mechanisms. The friction coefficients of the composite are ~0.7 below 400°C but decrease sharply to ~0.18 above 500°C. Characterisations of this composite indicate that several silver molybdates (Ag₂MoO₄, Ag₂Mo₂O₇ and Ag₂Mo₄O₁₃) formed from oxidation of Ag–Mo composite at high temperatures benefit lubrication effects and lead to the decrease of friction coefficients. Formation mechanism of these silver molybdates during oxidation and wear was therefore studied, and a model based on solid reaction processes in the Ag–Mo–O₂ system was promoted. Copyright © 2015 John Wiley & Sons, Ltd.     

Traction of Lubricated Rolling Contacts between Thin-Film Coatings and Steel

Tribological thin-film coatings can enhance the performance of mechanical components such as bearings and gears. Although a lubricant is present in most applications, the interactions of the lubricant with the coated surfaces are not always well understood. In the present study, Stribeck curves (i.e., traction coefficient vs. dimensionless film thickness λ) were generated for lubricated rolling contact between coated and uncoated surfaces. Chromium nitride, tungsten carbide–reinforced amorphous hydrocarbon, and silicon-incorporated diamond-like carbon coatings were evaluated. Compositions, hydrogen concentrations, Raman spectra, and surface energies are reported for the films. A ball-on-flat test configuration was used in 5%, 50%, and 100% slide-to-roll conditions. The test lubricant was a polyalphaolefin containing rust and oxidation inhibitor additives only. Differences in traction performance were observed for different coating types. Traction coefficients decreased at high λ with increased hydrocarbon content in the coating. Coating micro-texture and composition were believed to influence traction as λ became small.     

Reductive performance of ZVI/Cu polyscale particle to decolorize reactive black 5

Based on direct reducing of copper ions by commercially available zero valent iron (ZVI), ZVI/Cu polyscale particles with high activation are synthesized and exhibit significant removal efficiency for reactive black (RB) dye. The ZVI/Cu polyscale particles could maintain a good performance for RB removal at a wide pH range of 3.0–9.0. Different from the mineralization process of other organic pollutants in ZVI/Cu system, the degradation kinetics of RB could be described well by novel pseudo‐second kinetic models. Results of scanning electron microscopy (SEM), X‐ray fluorescence elemental analysis (EDX), and X‐ray diffraction (XRD) show the planting Cu has deposited on the surface of Fe⁰. The characterization of ZVI/Cu particles and RB solution before and after degradation reveals that decolorization of RB is not only resulted from the reduction process including direct reduction by accepting electrons from Fe⁰ oxidation and indirect reduction by atomic hydrogen generated on the ZVI/Cu surface, but also the oxidation of hydroxyl radicals in the mineralization procedure of RB dye.     

The effect of an Ni–Cr protective layer on cyclic oxidation of Ti3Al

The effect of an 80Ni?20Cr (at.%) metallic coating on the cyclic oxidation behaviour of a Ti₃Al‐based alloy with the composition Ti?25Al?11Nb (at.%) was investigated in this study. Cyclic oxidation tests were carried out in air at 600 °C and 900 °C for 120 h. For one cycle test, the specimens were held for 24 h at test temperature and then furnace‐cooled to room temperature. The oxidation rate was determined by plotting the mass gain per unit surface area of the specimen vs. exposure time. The morphology and composition of the oxidation products were characterized on the cross‐section of the specimens by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and atomic force microscopy. The oxidation scale forms during exposure at both 600 °C and 900 °C. TiO₂ is the main oxide component, whereas the Al₂O₃ layer appears only discontinuously. The remarkable improvement in oxidation resistance at 900 °C was attributed to the chemical composition and structure of the scale formed on the 80Ni?20Cr coating.     

Extending the retention of friction‐reducing capability in low‐phosphorus engine oils

In advanced fuel‐efficient engine oils containing molybdenum dialkyldithiocarbamate, Mo(dtc)₂, as a friction‐reducing additive, the friction‐reducing capability is gradually depleted with mileage accumulation and is dependent on the presence of other additives, such as zinc dialkyldithiophosphate, Zn(dtp)₂. Indeed, it has been shown that the loss of the friction‐reducing capability of Mo(dtc)₂ coincides with the depletion of Zn(dtp)₂. The next generation of oils will specify a lower phosphorus content (e.g., 0.08% in ILSAC GF‐4 and even lower in the specification after GF‐4) to reduce the detrimental effects of phosphorus on catalyst systems. This will necessitate the use of less Zn(dtp)₂, which could have an adverse effect on the retention of friction‐reducing capability. The aim of this study was to determine if the retention of friction‐reducing capability could be maintained or even increased at 0.05% phosphorus with newer molybdenum trinuclear, Mo₃S₇(dtc)₄, additives. To facilitate the study, a modified laboratory‐based ageing test was developed which correlated with the loss of friction‐reducing capability in the Sequence VIB engine test. This ageing test was used to evaluate model blends of Mo₃S₇(dtc)₄ with Zn(dtp)₂ at 0.05% phosphorus and added antioxidants. The results indicate that it is possible to extend the retention of friction‐reducing capability. However, whether or not it can be extended beyond the current drain intervals is still an open question.     

Studies on Degradation Mechanisms of Tape Lubricants in a High Vacuum Environment

Degradation and tribological performance of several tape lubricants were studied during sliding in a high vacuum environment. Gaseous products generated from the head–tape interface and friction force were detected and monitored as function of sliding distance by using a quadrupole mass spectrometer and strain gauges. Chemical analyses of the commercial tape lubricants were done to better understand the degradation processes and degradation products in the sliding tests. Experimental results showed that the commercial metal evaporated (ME) tape lubricants include fatty acid and perfluoropolyether (PFPE) compounds. The degradation products from the commercial tape include small fluorine containing fragments from the PFPE lubricant and small hydrocarbon fragment from fatty acid. In addition, three other species, H₂, C₂H₅ and CO₂ were detected in the case of ME tapes and they were generated from the degradation of the diamond-like carbon (DLC) coating on the tape surface. The commercial metal-particle (MP) tape used fatty acid and fatty acid ester lubricants. Only hydrocarbon fragments were detected in the MP tapes' sliding tests, no H₂, C₂H₅ and CO₂ were found. The coefficient of friction of these two tapes increased with sliding and depletion of lubricant on the tape surface. The trend of the coefficient of friction was different for ME and MP tapes because of the differences in the lubricant and lubricant distribution on these two tape surfaces. Z-Dol and stearic acid were used to lubricate ME tapes, their test results were analyzed and compared with the commercial tapes' test results.     

Synergistic effect of diisopropyl phosphite and over‐based calcium sulphonate additives on tribological properties of AISI 52100 steel/Al2O3 ceramics

The friction‐reducing and anti‐wear effect of the 500SN base oil containing diisopropyl phosphite (T451) and over‐based calcium sulphonate (KT5447) on AISI 52100 steel/Al₂O₃ ceramic were investigated with a ball‐on‐disc tribometer at a light load of 200 N and a high load of 400 N. The results indicate that the 500SN base oil containing T451 and KT5447 appears to have a synergistic effect on the pair. For the light load of 200 N, the effective composition is 3 wt% T451 + 2–3 wt% KT5447. For the high load of 400 N, the combination of T451 and KT5447 appears to have a synergistic friction‐reducing and anti‐wear effect. The scanning electron microscope images show that ploughed grooves, pitting, spalling and corrosion are the dominant wear modes for both 200 and 400 N. However, no evidence for the formation of the expected sulphur‐containing or phosphorus‐containing chemical compound is found according to X‐ray photoelectron spectroscopy analysis of the worn steel ball surface at both loads. Copyright © 2011 John Wiley & Sons, Ltd.     

European ecolabels for biodegradable hydraulic oils — a challenge to base material producers and formulators

‘Ecolabels’ are a means to guide the user to more environmentally favourable products. With regard to lubricants, the German Blue Angel UZ‐79 and the Swedish standard SS 155434 for biodegradable hydraulic fluids are perhaps the most important. Whereas the Blue Angel is optional, the Swedish standard SS 155434 is a legal requirement: hydraulic fluids not fulfilling the criteria of SS 155434 are not permitted on the Swedish market. Version 4 of SS 155434, which came into effect in July 2000, introduced new and more stringent ecological requirements. In view of the growing importance of the Swedish market for biodegradable hydraulic oils, the authors' company launched a research programme in early 2000 with the aim of offering SS‐155434‐compliant oleochemical base oils by the end of the year. First, the effects and the plausibility of the new assessment criteria for the ready biodegradability of raw materials were studied. A systematic comparison based on chemical oxygen demand (COD) and theoretical oxygen demand (ThOD) evaluations confirmed that unqualified reliance on the COD parameter can lead to false positive evaluations. The studies also showed, however, that results based on COD determined by chemical analysis are valid, provided a suitable oxidation method is used and the completeness of the oxidation is carefully monitored. Moreover, it was shown that the required use of the reference parameter ThOD does not necessarily require complicated elementary analyses of the test substance. Even in the case of oleochemical products with indefinable structural formulas (C‐chain fractions, alkoxylated compounds), structural estimates enabled sufficiently accurate ultimate oxidation values to be calculated. The studies also showed that the restriction to only two degradation test methods is scientifically unfounded. An extension of the approved test methods to include the scientifically accepted CO₂ headspace test and two‐phase closed bottle test would enable existing data to be used without detracting from the environmental standard. On the basis of more recent degradation studies, it has been shown that synthetic esters, especilay various saturated and unsaturated TMP fatty acid esters, satisfy the stringent sriteria of the new SS 155434, Supplementary studies of low‐viscocity XXX‐oils (hydrocrackates) and mixtures of XXX‐oils and synthetic esters indicated that this product class could be optimised to make it satisfy the criteria of the Swedish ecolabel.     

Tribological performance of an ionic liquid as a lubricant for steel/aluminium contacts

The wear and friction behaviour of an ionic liquid 1‐ethyl‐3‐hexylimidazolium tetrafluoroborate (L206) was investigated as a lubricant for steel/aluminium contacts using an Optimol SRV® oscillating friction and wear tester. The elemental composition and chemical nature of the antiwear films generated on the aluminium surface were analysed using a scanning electron microscope with a Kevex energy dispersive X‐ray analyser attachment (SEM/EDS) and X‐ray photoelectron spectroscopy (XPS). A low friction coefficient (˜0.05) was recorded when lubricating with L206; a small amount of water (5 wt. %) in L206 effectively reduced the wear volume and greatly increased the microhardness of the aluminium alloy, but had little effect on the friction coefficient. The SEM/EDS results showed that severe corrosive wear occurred on the aluminium alloy when lubricating with neat L206, which could be avoided by the addition of water in L206. The XPS results indicated that the species AlF₃, Al₂O₃, AlO(OH), and Al(OH)₃ formed during friction; there was no indication of boron on the worn surfaces.     

Antifriction and Antiwear Properties of an Ionic Liquid with Fluorine-Containing Anion Used as Lubricant Additive

Tribological behavior of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl) imide [P₆₆₆₁₄][NTf₂] ionic liquid (IL) used as additive in a diester oil at concentrations of 0.25, 0.5 and 1 wt% was studied in this research. The IL solubility in the base oil was measured using the inductively coupled plasma mass spectrometry (ICP-MS) technique, and corrosion analysis was done at room temperature at relative humidity of 49–77%. Tribological tests were conducted for 30 min at room temperature, 15 Hz frequency, 4 mm of stroke length, a load of 80 N (corresponding to 2 GPa of maximum contact pressure) and relative humidity of 35–53%. Friction coefficient was recorded during tests, and the wear scar was measured by confocal microscopy. Worn surface was also analyzed by SEM, EDS and XPS. Results showed that a saturated solution of [P₆₆₆₁₄][NTf₂] in the base oil contains about 30 wt% of IL and corrosion activity for the highest concentration of IL (1 wt%) was not found after a 20-day test. Although the base oil and the mixtures had similar friction behavior, only the 1 wt% sample exhibited slightly lower wear volume than the base oil. SEM images exhibited similar wear track width (707–796 µm) and wear mechanism (adhesive) for all samples tested. In addition, the EDS spectra only showed the elements present in the steel. Finally, the XPS measurements could not detect differences regarding iron chemical state among the samples, which is consistent with the tribological behavior obtained.