Influence of metallic and oxidized iron/steel on the reactivity of triphenyl phosphorothionate in oil solution

The influence of metallic and oxidized iron/steel on the reactivity of triphenyl phosphorothionate (TPPT) in oil solution at 473 K was investigated by means of FT-IR, NMR and XPS. The FT-IR and NMR results show that the degradation of TPPT was catalyzed by metallic and oxidized iron powder and started with the breakage of the PS bond to form triphenyl phosphate (TPP). The results of the XPS sputter depth profile show the multilayer structure of the thermal film formed on 100Cr6 steel filings immersed for 72 h in TPPT solution heated at 473 K.     

Reactivity of Triphenyl Phosphorothionate in Lubricant Oil Solution

Investigating the thermo-oxidative reactivity of anti-wear additives in lubricant oil solution at high temperature can significantly contribute to an understanding of the mechanism of thermal film and tribofilm formation on metal surfaces. In this study, the reactivity of triphenyl phosphorothionate (TPPT) in lubricant oil solution at high temperature (423 and 473 K) has been studied by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The results show that the TPPT molecule was highly thermally stable and did not completely decompose in oil solution even upon heating at 423 K for 168 h and at 473 K for 72 h. The degradation of the TPPT molecule, which turned out to be a first-order reaction, started taking place after 6 h at both temperatures, leading to the breakage of the P=S bond with the formation of triphenyl phosphate. During these heating experiments, no oil-insoluble compounds were detected. The oxidation of the base oil as a result of the prolonged heating demonstrated that the TPPT molecule did not effectively act as oxidation inhibitor.     

Reactions of zinc-free anti-wear additives in DLC/DLC and steel/steel contacts

In this work, the ability of ashless anti-wear additives to form protective tribofilms on diamond-like carbon (DLC) and steel surfaces was investigated and compared to the reactions of ZnDTP. Reciprocating sliding tests were performed under mild tribological conditions for steel/steel and DLC/DLC contacts to avoid wearing through the DLC coating. A comparison of the friction behavior of ZnDTP with two ashless additives, a butylated triphenyl phosphorothionate (b-TPPT) and an amine phosphate (AP), indicated that the latter additive behaved in a different manner to the first two. b-TPPT shows the lowest friction coefficient for DLC/DLC contacts whereas the AP give the lowest friction coefficient for steel sliding against steel. AFM and ESEM were performed to analyze the surfaces and showed the build up of tribofilms from ZnDTP and b-TPPT onto both the steel and DLC surfaces. No evidence of such a film formation on DLC was observed when the AP were used.     

Friction of molybdenum disulfide–titanium films under cryogenic vacuum conditions

The tribological behavior of steel and sapphire sliding on a sputtered MoS₂+Ti coating was studied in ultra-high vacuum as a function of temperature over the range of 4–300 K. The coefficient of kinetic friction for the steel/moly interface was determined to be approximately 0.05 from room temperature to 240 K, and increased monotonically to 0.125 at 4 K. The sapphire/moly friction coefficient was measured to be 0.15±0.05 at room temperature and increased monotonically to 0.25 at 4 K. We also analyze in detail the flash temperature due to frictional heating at the sliding contacts. Flash heating is a particularly strong effect at cryogenic temperatures.     

Atomistic investigation of process parameter variations on material deformation behavior in nanoimprint lithography of gold

Direct metal nanoimprint (NIL) of the gold substrate by silicon mold has been investigated through molecular dynamics simulations. The effects of different process parameters such as imprint temperature, mold velocity, and mold profile on the contact pressure, von Mises stresses, and dislocation behavior of the lattice structure was studied during the nanoimprinting process. Higher contact pressures were observed during the molding phases which further declined during the relaxation and demolding phases. The narrow mold geometry (aspect ratio = 2) had the highest contact pressure (6.61 GPa) at 1300 K and 50 m/s due to the lower cross-sectional area and incompressible nature of the gold atoms. The maximum von Mises stress (1.8 × 10⁷ GPa) was observed under the mold tooth during the insertion phase at 298 K and 473 K. Further, the highest von Mises stress (1.32 × 10⁷ GPa) was tracked at 1300 K due to the restraining effect of the mold on the expanding molten gold atoms. The lattice dislocation analysis using the polyhedral template matching (PTM) method revealed that the gold substrate maintains its face centered cubic (FCC) structure and consequent ductile nature after the NIL process at 298 K and 473 K, respectively. At 1300 K, for both mold profiles more than 60% of gold atoms remained with distorted structure after completion of NIL process due to the melting and rapid crystallization of the gold atoms. High-resolution imprints were achieved at the recrystallization temperature (473 K) of gold for both the mold geometries.     

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

Abstract

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

The properties of various antiwear and extreme‐pressure additives in pentaerythritol ester

The tribological properties of three representative antiwear and extreme‐pressure additives, tricresylphosphate (TCP), triphenylthiophosphate (TPPT), and α‐mercaptobenzothiazole (MBT), in pentaerythritol ester at different concentrations were studied. It was found that TCP could react with Fe to form an organic phosphate film containing 4% P on the scar surface, while TPPT formed a blended organic phosphate and inorganic FeS film, containing 4% P and 6% S, respectively. MBT formed an inorganic FeS film containing 45% S. Ferrographic analyses of wear particles collected from oil samples after four‐ball tests showed that the higher the temperature the better the tribological performance of the additivated ester, due to its reaction with the metal surface.     

In Situ Attenuated Total Reflection (ATR/FT-IR) Tribometry: A Powerful Tool for Investigating Tribochemistry at the Lubricant–Substrate Interface

To investigate the chemical changes occurring at metal/lubricant interfaces under tribological conditions in the boundary-lubrication regime, an in situ system for conducting quantitative tribological measurements has been constructed by combining an attenuated total reflection Fourier-transform infrared (ATR/FT-IR) spectrometer with a reciprocating tribometer. By periodically acquiring ATR/FT-IR spectra during sliding, spectroscopic changes due to thermal and/or tribochemical reactions occurring at the metal/oil interface can be monitored and correlated with friction measurements. The usefulness of this tribological test system has been demonstrated by performing ATR tribological experiments in the presence of a poly-α-olefin base oil at high temperature (423 K) on iron-coated germanium ATR crystals.     

Abrasive wear resistance of textured steel rings

The fundamental aim of the present research is to study the effect of dimple shape and area density on abrasive wear in lubricated sliding. The other aims are to recommend a method of obtaining the local linear wear of a textured ring on the basis of profilometric measurement and to analyse the changes in the surface topography of this ring with selection of parameters that could monitor the “zero-wear” process.The experiments were conducted on a block-on ring tester. The stationary block made from cast iron of 50 HRC hardness was ground. The rotated ground ring was made from 42CrMO4 steel of 32 HRC hardness. The rings were modified by a burnishing technique in order to obtain surfaces with oil pockets. Oil pockets of spherical and of drop shape were tested. The pit-area ratios were in the range: 7.5–20%. The tested assembly was lubricated by oil L-AN 46. Because of the great hardness of the co-acting parts the wear resistance test was carried out under artificially increased dustiness conditions. The dust consists mainly of SiO₂ and Al₂O₃ particles. Measurement of local microscopic ring wear was made using a three-dimensional scanning instrument. The tendencies of ring surface topography changes during wear were analysed. Various methods of obtaining the local wear value during a low wear process were proposed and compared. We found that a spherical shape of dimples was superior to a drop shape with regard to wear resistance of steel rings.     

硫代磷酸三苯酯在季戊四醇酯中摩擦学性能及作用机理的研究

使用四球试验机，Falex摩擦试验机，铁谱技术和俄歇电子能谱技术考察了硫代磷酸三苯酯（TPPT）在季戊四醇酯中的摩擦学性能，研究表明：硫代磷酸三苯酯是良好的极压添加剂，很小的添加量就能起到良好的抗极压作用；而起抗磨作用时，必须满足一定添加量的要求，这是因为TPPT是必须在一定的高温下才能起作用的添加剂，在极压试验条件下，因摩擦产生的温升比常磨试验要大，因此TPPT的感受性更好，文章最后对TPPT的作用机理也进行了一定的推测。     

Improving tribological behaviour of piston ring–cylinder liner frictional pair by liner surface texturing

Experiments were carried out on a reciprocating tester. The lubricant was supplied into the inlet side of the contact zone. The construction of tribological tester allows to measure the friction force between specimen and counter-specimen. Tribological behaviours of cylinder liners with and without oil pockets were compared. Specimens were cut from plateau honed cylinder liners made of grey cast iron. Counter-specimens were cut from grey cast iron piston rings. A special tool acted as a hammer to form additional dimples on the liner surfaces. The area density of oil pockets was about 13%. Specimen surfaces had dimples with average depths about 5 μm and diameters in the range 0.15–0.2 mm. Two batches of tribological tests were carried out, in regimes of full and starved lubrication. Friction tests were conducted at three mean sliding speeds: 0.44, 0.66 and 0.88 m/s. Experiments were performed with normal load in the range 50–300 N, starting from the lowest load. Normal load increased in a stepwise manner after 2 min at each load, until the maximum load was reached. Areal surface topographies of specimens and counter-specimens were measured before and after two batches of tests by white light interferometer.     

The Influence of Lead Suspension in Oil Lubricant on the Sliding Wear Behaviour of Cast Iron

This investigation pertains to the analysis of the sliding wear response of a cast iron over a range of applied pressures in the presence of an oil lubricant. The effect of varying concentrations of lead particles suspended in the oil lubricant on the wear behaviour of the cast iron was also examined. The wear rate increased with pressure initially at a lower rate followed by a higher rate of increase beyond a specific pressure. Furthermore, the presence of suspended lead particles up to a specific concentration in the oil proved beneficial while the trend reversed at still higher concentrations. The extent of frictional heating increased with test duration at a high rate in the beginning of the tests. This was followed by a reduced rate of temperature increase at longer test durations. In some cases, the rate of temperature rise increased once again while it reduced in one case towards the end of the tests. The severity and extent of frictional heating also increased with pressure. Lead addition to the oil lubricant up to a specific concentration led to a reduced degree of heating while the trend reversed at still higher lead contents. Specimen seizure caused significantly high wear rate and frictional heating. The observed wear response of the samples has been explained in terms of specific characteristics like cracking tendency and lubricating and load bearing capacity of various microconstituents of the specimen material. Another important factor of concern affecting wear characteristics was observed to be lubricating film formation and its stability during sliding. The wear behaviour has also been substantiated through the characteristics of wear surfaces and subsurface regions.     

Low-friction tribofilm formed by the reaction of ZDDP on iron oxide

An iron oxide layer (mixture of Fe₃O₄ and FeO) was formed by water-vapor treatment on tool steel plates. Bearing steel cylinders were slid against the plates in PAO with and without 1% zinc dialkyldithiophosphate (ZDDP) at 80 °C. The friction coefficient was below 0.06–0.08 with ZDDP, which is more than 20% lower than that without ZDDP and about a half of a steel/steel contact under the same condition. The formation of multi-layered tribofilm of 30–130 nm on the iron oxide was identified by TEM. The bottom part of the tribofilm is a layer of 10–30 nm that contains Zn, Fe, S, P, and O with a gradient composition, where distribution peaks of Zn and S were found by EDX.     

Effect of Surface Oxide Layer of Steel on the Tribological Characteristics of Load-bearing Additives for Multiply-Alkylated Cyclopentane Oil under High Vacuum

The tribological performance of two types of additives—alkylated phenyl phosphate and lead naphthenate—dissolved in multiply-alkylated cyclopentane was evaluated under a high vacuum using two types of ball-on-disk tribometers: a reciprocating motion tribometer under mild loading conditions and a unidirectional rotating motion tribometer under heavy loading conditions. A ball and a flat disk made of SUS440C stainless steel were used as specimens for both tribometers. The surface of the as-received flat disk specimen was covered with a thick (>40 nm) oxide layer. For the examination of the effect of the surface oxide layer on the tribological performance of the liquid lubricants under a high vacuum, another specimen with an oxide layer (approx. 4 nm thick) was prepared. The alkylated phenyl phosphate additive showed better lubrication performance with the specimen with the thicker oxide layer, but the lead naphthenate additive showed superior performance with the thinner oxide layer specimen. It is also shown that these opposite tribological characteristics are explained by the hard and soft acids and bases principle.     

Effectiveness of an externally added solid lubricant on the sliding wear response of a zinc–aluminium alloy,its composite and cast iron

The role played by an externally added solid lubricant like graphite towards controlling the sliding wear behaviour of a zinc-based alloy has been examined in this study. The influence of dispersing hard silicon carbide particles in the alloy was also investigated by testing the composite in identical test conditions. The wear performance of the zinc-based alloy and its composite was compared with that of a gray cast iron. Wear tests were performed in oil lubricated environment. Composition of the lubricant was changed by adding various quantities of graphite (particles) to the oil. The study suggests that the wear response (in terms of wear rate, frictional heating and friction coefficient) of the samples improved in the presence of suspended graphite particles in the oil lubricant. However, this improvement was noticed up to a critical content of graphite particles only and the trend reversed at still higher graphite contents. The zinc-based (matrix) alloy revealed highest wear rate. Dispersoid silicon carbide particles showed a significant improvement in the wear performance of the matrix alloy. The cast iron performed in between the matrix alloy and composite. The frictional heating and friction coefficient were the highest for the composite while the cast iron and the matrix alloy showed a mixed response. Examinations of wear surfaces, subsurface regions and debris particles helped to substantiate the observed wear response of the samples.     

Friction of molybdenum disulfide-titanium films under cryogenic vacuum conditions

The tribological behavior of steel and sapphire sliding on a sputtered MoS₂+Ti coating was studied in ultra-high vacuum as a function of temperature over the range of 4-300 K. The coefficient of kinetic friction for the steel/moly interface was determined to be approximately 0.05 from room temperature to 240 K, and increased monotonically to 0.125 at 4 K. The sapphire/moly friction coefficient was measured to be 0.15±0.05 at room temperature and increased monotonically to 0.25 at 4 K. We also analyze in detail the flash temperature due to frictional heating at the sliding contacts. Flash heating is a particularly strong effect at cryogenic temperatures.     

Thermal optimization and supercapacitive application of electrodeposited Fe2O3 thin films

In the present work, thin films of Fe₂O₃ were deposited onto stainless steel substrates by electrodeposition method. All deposited electrodes were annealed for 1 h within the temperature range of 423–673 K with an interval of 50 K. These were further characterized for their structural and morphological measurements by means of X-ray diffraction and scanning electron microscopy techniques, respectively. The supercapacitive characteristics of as-deposited and annealed electrodes were carried out in 1 M KOH electrolyte to confirm the variation in specific capacitance, specific energy, specific power and columbic efficiency, etc., with annealing temperatures.     

Sliding wear response of a cast iron under varying test environments and traversal speed and pressure conditions

This study pertains to the examination of sliding wear behaviour of a gray cast iron over a range of sliding speeds and applied pressures in dry and (oil and oil plus graphite) lubricated conditions. Wear properties characterized were wear rate and frictional heating. The cast iron revealed various forms and sizes of graphite particles in a matrix of pearlite and limited quantity of free ferrite. Different solidification patterns, as controlled by the chemical composition and/or carbon equivalent of the alloy and rate of cooling, were thought to be responsible for the varying morphology of the graphite phase formed in the material matrix. Occasional decohesion of graphite at ferrite/graphite interfacial regions was also observed.The wear rate of the cast iron increased with the speed and pressure of sliding due to increasing severity of wear condition. The specimens tended to lose proper contact with the disc at larger pressures when slid dry. This was attributed to severe cracking tendency of the material. On the contrary, specimen seizure was noticed in the oil and oil plus graphite lubricated conditions; the seizure resistance (pressure) decreased with sliding speed in presence of the lubricants. The wear rate versus pressure plots attained different slopes, i.e. the rate of increase in wear rate with pressure, depending on the test environment. One slope and inappreciable effect of pressure on wear rate were noticed due to substantial cracking tendency of the cast iron when tested in dry condition. In the oil lubricated condition also, virtually one slope was observed but it was higher than that in dry condition indicating greater sensitivity of wear rate towards the applied pressure. Also, the samples attained lower wear rate in oil than in dry condition in view of suppressed cracking tendency causing more stable lubricating film formation in presence of the oil lubricant. Addition of graphite particles to the oil lubricant caused a further reduction in wear rate because of the enhanced possibility of a more stable lubricant film formation due to smearing of the graphite particles. In this case, the slope of the wear rate versus pressure plots was the least in the intermediate range of pressures irrespective of the sliding speed owing to more stable lubricating film formation.A higher rate of temperature increase with test duration (intermediate sliding distance) in the beginning was attributed to the abrasive action of the hard debris generated through the fragmentation of the initially contacting asperities. A subsequently observed lower rate of increase at longer durations could be owing to the occurrence of mild wear condition in view of less stressing of the contacting asperities and increased stability of the lubricant film formed. Increase in the rate of frictional heating at still longer durations resulted from destabilization of the lubricating film.Frictional heating increased with applied pressure and sliding speed in view of increasing severity of wear condition. The rate of increase in frictional heating was low initially up to a specific pressure followed by a higher rate of increase at still larger pressures when the tests were conducted in oil plus graphite at both the sliding speeds and in the oil lubricant at the lower speed. A constant (high) rate of increase in frictional heating with pressure was noticed in the dry condition at both the sliding speeds and in the oil lubricant at the higher speed. Low rate of frictional heating with pressure was attributed to the occurrence of mild wear condition while a higher rate of frictional heating with pressure resulted from the occurrence of severe wear condition. As far as the influence of test environment on frictional heating is concerned, least frictional heat was generated in the oil plus graphite lubricant mixture while the maximum was noticed in dry condition, intermediate response of the samples being observed in oil. Formation of more stable lubricating film was thought to be responsible for lower frictional heating in the lubricated conditions; the presence of graphite in the oil lubricant increased the extent of lubricating film formation and stability of the film so formed.The wear response of the samples has been explained in terms of cracking tendency and lubricating effects of graphite, predominance of the counteracting effects of the two parameters over each other, and lubricating film formation by the external oil (plus graphite) lubricant on the sliding surfaces in specific test conditions. Characterization of wear surfaces, subsurface regions and debris particles of the material enabled to further substantiate the observed wear performance of the samples.     

Dimples shape and distribution effect on characteristics of Stribeck curve

A purpose of this research is to study the influence of geometrical characteristics of the surface texture on the Stribeck curve in lubricating sliding.The tribosystem consists of the stationary block pressed at the required constant load 1800 N against the ring rotating at the defined speeds. Tests were conducted at increasing sliding speed of range 0.08–0.69 m/s. Every speed was maintained for 2 min. The test was carried out under conformal contact conditions. The sliding was unidirectional. The block was a part of a bearing sleeve hardened EN-GJS 400-15 cast iron with a hardness value of 50 HRC. The ring samples, 35 mm in diameter, were made from hardened 42CrMo4 steel of hardness 32 HRC. Some variants of specimen surfaces were created by burnishing technique. The area density of oil pockets S was in the range 7.5–20%. The dimples depth to length ratios were between 0.03 and 0.08. Ring surfaces with oil pockets of short drop, long drop and spherical shapes were tested.It was shown that with proper shape and dimensions as well as suitable area density of oil pockets the friction characteristic of the sliding pairs could be improved in comparison to non-textured surfaces.     

Adhesive wear of stir cast hypereutectic Al–Si–Mg alloy under reciprocating sliding conditions

This paper describes an attempt to enhance the wear properties of hypereutectic cast aluminium–silicon alloys produced by semi-solid metal (SSM) processing technique. The rheological experiments on SSM slurries were performed under continuous cooling condition from liquidus temperature. Wear characteristics of alloy under investigation were studied using pin on flat wear system over a range of normal load (10–40 N) at constant average sliding speed (0.2 m/s) against cast iron and stainless steel counter surface. Stir cast alloy showed lesser weight loss compared to conventional cast alloy. Stir cast and conventional cast alloys showed higher weight loss against the stainless steel as compared to that against cast iron counter surface. Optical microscopy of the conventional cast and stir cast hypereutectic alloy has shown that stir casting causes refinement of primary silicon particles and modification of eutectic silicon compared to conventional cast alloy. The scanning electron microscopy of wear surfaces was carried out to investigate the mode of wear.