Molecular dynamics simulation of surface energy and ZDDP effects on friction in nano-scale lubricated contacts

Molecular dynamics simulations are used to study the tribological performance of a lubricant mixture containing hexadecane base oil and 5% zinc dithiophosphate (ZDDP) under molecular confinement conditions. The influence of ZDDP additive and the surface-lubricant interaction on the mechanical and thermal interfacial response are studied in detail. Results show that mechanical and thermal slips are reduced by increasing the surface energy. Simulations also demonstrate the migration of ZDDP molecules and their adsorption onto the solid surface resulting in a remarkable suppression of mechanical slip compared to pure hexadecane. Consequently, the effective shear rate is higher and so is the friction.     

An Adsorption Model for Friction in Boundary Lubrication

A model describing the relationship between friction coefficient and surface adsorption of a two-component lubricant (i.e. base lubricant and one additive) is developed for boundary lubrication. This model relates the coefficient of friction to the extent of metal-metal contact or, inversely, the fractional surface coverage of the lubricant. Using a suitable adsorption isotherm, an expression for friction coefficient is obtained, relating the friction coefficient to the additive concentration and the adsorption energy. The proposed model and the selected adsorption isotherm are experimentally verified by testing several model additives in a petroleum-base lubricant. An excellent correlation is obtained between the adsorption-free energies calculated from the friction coefficient data and the adsorption-free energies determined from adsorption studies. The ranking order of additives based on friction coefficient is explained in terms of the molecular structure and the structural effects on the adsorption-free energy.     

The lubricant migration rate on the hard disk surface

The optical surface analyzer (OSA) was found to be an excellent tool to examine the lubricant migration rate on thin film disks. Using the OSA it was found that the rate of lubricant migration increased as molecular weight decreased. An AM type perfluoropolyether with an aromatic end group and Z-Dol were also observed to have different migration rates for the same molecular weight. The migration rate of AM lubricant was increased significantly by the presence of X-1P as an additive in the lubricant system.     

Scuffing of Area Contacts Under Starved Lubrication Conditions

The scuffing behavior of 390-T6 and DHT3 aluminum alloys, Si-Pb brass and gray cast iron, sliding against 1018 carburized steel, is experimentally studied under starved lubrication conditions. The major emphasis of the study is on the 390-T6 aluminum alloy. All tests are conducted in a high pressure tribometer (HPT) under RI34a (tetrafluoroethane) environment with polyalkylene glycol (PAG) and polyolester (POE) lubricants to simulate failures of critical tribocontacts in refrigerant compressors. An area contact, pin-on-disc geometry, is used to examine the effects of degree of lubricant starvation, sliding velocity, materials, and lubricant/refrigerant mixtures on scuffing. The scuffing transitions characteristics of 390-T6 aluminum as a function of lubricant supply rate are also examined. The processes leading to scuffing and failure mechanisms are studied by examination of scuffed surfaces and subsurfaces. Based on the experimental observations, it is hypothesized that bulk material failure during scuffing is due to plastic shearing or smearing.     

Lubrication Properties of Polyalphaolefin and Polysiloxane Lubricants: Molecular Structure–Tribology Relationships

This study investigates the rheological properties, elastohydrodynamic film thickness, and friction coefficients of several commercially available polyalphaolefin (PAO) and polydimethylsiloxane (PDMS)-based lubricants to assess relationships between molecular structure and lubricant performance. Molecular structures and masses were determined by nuclear magnetic resonance spectroscopy and gel permeation chromatography, respectively. Density and viscosity are measured from 303 to 398?K, while elastohydrodynamic lubricant film thickness and friction measurements were made at temperatures, loads, and speeds that are representative of boundary, mixed, and full-film lubrication regimes. The results show that PDMS-based lubricants are thermally and oxidatively more stable than PAOs, while the viscosity of PDMS-based lubricants is generally less temperature sensitive than PAOs, except for highly branched polysiloxanes. In particular, this study provides quantitative insight into the use of PDMS-based lubricants to obtain low friction through the entire lubrication regime (boundary to full film) by optimal tuning of the molecular mass and chain branching.     

Tribological performance of modified jatropha oil containing oil-miscible ionic liquid for machining applications

Modifying physicochemical and tribological properties of a bio-based lubricant is essential in improving its lubrication performances. This paper presents the effectiveness of a fully oil-miscible Ionic liquid (IL) as lubricant additive into a bio-based lubricant. Methyltrioctylammonium bis(trifluoromethylsulfonyl)imide (AIL) was selected as IL additive to improve the tribological performance of the biobased lubricant. Additive was mixed into the bio-based lubricant at three levels of mass concentrations (1 wt.%, 5 wt.% & 10 wt.%). Tribology tests on steel/steel contacts were conducted to evaluate the lubricant samples. Test outputs were benchmarked against the neat bio-based lubricant. Results revealed good synergistic effect of the AIL additive blended into the bio-based lubricant. MJO+AIL10 % has shown good corrosion inhibition, superior friction reduction (48 %), lower worn surface area (23 %), excellent surface finish (46 %) and increased tapping torque efficiency (8 %). MJO+AIL10 % provided excellent tribological performances which corresponds to the energy saving and environmental benefit for sustainable machining applications.     

Tribological Study Comparing PAG and POE Lubricants Used in Air-Conditioning Compressors under the Presence of CO2

Polyalkylene glycol (PAG) and polyolester (POE) synthetic lubricants are good candidates for air-conditioning systems that work with alternative refrigerants such as carbon dioxide (CO₂). Both synthetic lubricants are widely used in air-conditioning compressors and have been optimized for use with hydrofluorocarbon (HFC) refrigerants. However, it is still not clear which lubricant is more suitable for use in compressors operating with CO₂ as a refrigerant. This study compares the performance of PAG and POE lubricants of the same viscosity (ISO VG 68) used in air-conditioning compressors. The materials used were Al390-T6 disks and hardened steel SAE 52100 pins. The tests were performed using a high pressure tribometer (pin-on-disk configuration) in the presence of CO₂. The results showed that scuffing and wear resistance of Al390-T6 tested with PAG were superior compared to the samples tested with the POE lubricant. Chemical analysis using X-ray photoelectron spectroscopy showed that PAG tends to promote the formation of carbonate layers on the surface, leading to improvement in the tribological performance of the interface.     

Study of additive‐additive interactions in a lubricant system by NMR,ESCA, and thermal techniques

Engine oil lubricants are formulated with a variety of additive components at different dosages to obtain the desired physico‐chemical characteristics. Antiwear, friction modification/energy efficiency, dispersancy, and detergency properties are normally achieved by the use of zinc dialkyldithiophosphate (ZDDP), molybdenum dithiocarbamate (MoDTC) and ashless alkyl phosphorodithioate, polyisobutylene succinimide (PIBS), and metal sulphonates / phenates, respectively. It has been reported that these additives interact with each other and affect the overall performance of a lubricant system. The additive‐additive interactions have been studied by nuclear magnetic resonance (NMR) and infrared spectroscopic techniques, where attention has been mainly focused on the ZDDP‐PIBS additive system in the presence or absence of other additives. The results have been used to relate the synergistic or antagonistic effects of such interactions to the overall performance of a lubricant. Recently, MoDTC has found wider application in lubricants as a friction modifier and energy‐efficient additive. However, no studies of the additive‐additive interactions of the PIBS‐MoDTC‐ZDDP additive system using analytical techniques have been reported. The present paper covers the fundamental and mechanistic aspects of additive‐additive interactions of ZDDP, MoDTC, PIBS, and sulphonate / phenate additives present in a lubricant system as studied by ³¹P NMR, electron spectroscopy for chemical analysis (ESCA), and thermogravimetric analysis (TGA) techniques. ESCA, which is a surface analytical technique, has been used to provide basic evidence for the formation of various complexes through interactions occurring in the electronic binding energies of orbitals of various atoms of the additives. The ESCA studies have also revealed the actual atomic sites of interaction between the additives responsible for the formation of adducts or complexes. The differential scanning calorimetry profiles of blends have verified the interactions among the additives and shown that the stability of the additive system is quite different from that of the additives alone. The shifts in the ³¹P NMR signals, the changes in the binding energies of the s, p, and d orbitals of additive elements, and the multistage decomposition profiles in the TGA thermograms of interacting systems due to complexion and adduct formation have enabled a mechanism of interaction to be proposed.     

Dominant Factors in Lubricant Transfer and Accumulation in Slider-Disk Interface

Lubricant transfer from disk to slider and lubricant accumulation on slider are very important in designing a stable slider-disk interface of ultra-low spacing. In this article, the effects of different parameters on the lubricant transfer and accumulation are studied and the reasons behind the effects are explained. Furthermore, the time for the lubricant transfer to reach steady state is estimated. It is found that lubricant molecular weight plays a dominant role in the lubricant transfer and accumulation. Lubricant transfer and accumulation decrease dramatically with the increase in lubricant molecular weight. Lubricant transfer also strongly depends on lubricant thickness and bonding ratio on disk surface. A thinner lubricant and higher lubricant bonding ratio on disk surface reduce lubricant transfer obviously, which results in less lubricant accumulation. A diamond-like-carbon (DLC) overcoat of low adsorption area density on slider surface can reduce lubricant transfer and accumulation, especially for lubricant of low molecular weight. Lubricant accumulation increases with disk velocity and increases slightly with the decrease in slider flying height. Lubricant accumulation can be reduced by minimizing the area of slider pad. Lubricant transfer and accumulation become worse at higher ambient temperature. It takes seconds for lubricant of low molecular weight to reach steady transferred thickness and hours for lubricant of high molecular weight to reach the steady state.     

Effect of pressure and temperature on the molecular interaction of polar lubricant containing oleic acid in polypropylene glycol observed by infrared spectroscopy

In this work, we have investigated the infrared spectra of polar lubricant in order to explore the molecular interaction under high pressure and temperature conditions using diamond anvil cell. Polypropylene glycol and oleic acid were used as base oil and additive, respectively. Stretching vibration mode of polar functional groups, such as ν _O–H and ν _C═O, was found to be sensitive to pressure and temperature. The peak positions of the vibration mode were shifted clearly to lower wavenumber as pressure increases, and temperature increase induced a slight shift to higher wavenumber. These results indicate that hydrogen bonding between lubricant molecules of base oil and additive was influenced by pressure and temperature. And furthermore, the dependency of the peak shift was discontinuous and affected mainly by pressure. These results imply a structural change on the basis of the molecular interaction of the lubricating molecules at elastohydrodynamic lubrication contacts. Copyright © 2013 John Wiley & Sons, Ltd.     

水溶性润滑添加剂的分子设计浅说

本文提出了的水溶性润滑灰加剂的分子设计观点是：如果在一人上分子中同时具有亲水性、吸附性、反应活性等几类官能团及长碳链烃基，则可能兼具油剂和极压剂的功能，且能溶于水，成为性能优良的水溶性润滑添加剂，依据观点，根据四球机测试的实验数据，对几类物质的润滑性进行了讨论。     

两种不同润滑添加剂对车用二甲醚发动机性能影响的试验研究

开展了两种润滑添加剂对二甲醚发动机燃烧与排放特性影响的试验研究。结果表明:分别加入C100和R100这两种润滑添加剂后二甲醚发动机均可在宽广的转速和负荷范围内工作,其输出功率都可达到甚至超过原柴油机,但加入润滑添加剂R100时二甲醚发动机的输出功率、缸内最高爆发压力和最大压力升高率比加入润滑添加剂C100时的略高;加入两种不同润滑添加剂后二甲醚发动机都可以实现无烟燃烧,NOx、HC和CO排放相当。     

Additive Mechanism Investigation of Perfluoropolyether Lubricants with a Phosphazene Additive

The tribological characteristics of magnetic thin film media coated with perfluoropolyether (PFPE) lubricants (ZDOL and AM300J) and a phosphazene additive (X-IP) were investigated in this study. The drag test results show that under ambient and hot/wet conditions the media coated with AM300J lubricant have higher retention on the test track than those coated with ZDOL 2000 PFPE lubricant. The phosphazene additive X-IP was observed to strongly anchored to the surface and was not as easily removed as PFPE lubricants alone. The retention characteristics of X-IP are independent of either AM or ZDOL. Secondary Ion Mass Spectroscopy (SIMS) depth profile data and Angle-Resolved X-Ray Photo-electron Spectroscopy (XPS) reveal that X-IP molecules were distributed near the disk surface in the X-IP and PFPE lubricants mixed layer, indicating a strong bonding/adhesion of X-IP to the disk surface. Together with the drag testing data, the authors conclude that the preferential distribution of X-IP close to the disk surface in the mixed layer helps to improve lubricant retention performance at the head-disk interface.     

Structure effect of refrigeration polyolester oils for use in HFC-134a compressors

A study of polyolester oils (POE) for compressors using an ozone-friendly refrigerant is presented here. The effect of the chemical structure of POE was studied in relation to three lubricant properties: miscibility with HFC-134a (CF₃-CH₂F), lubricity (steel-on-steel and aluminium-on-steel contacts), and viscosity. The paper shows the strong structure effect of POE on miscibility and lubricity. Based on the data obtained, some model lubricants were blended, and the performance of these lubricants was assessed on refrigeration test rigs.     

Deactivation Effect of Tricresyl Phosphate (TCP) on Tribochemical Decomposition of Hydrocarbon Oil on a Nascent Steel Surface

A nascent surface has high activity to catalyze the decomposition of a lubricant under boundary lubrication conditions. To reduce the decomposition of a lubricant (multialkylated cyclopentane, MAC), tricresyl phosphate (TCP) was introduced as an additive. The tribological properties and decomposition process of lubricants on the nascent surface of bearing steel 52100 were investigated by a ball-on-disk friction tester in a vacuum chamber with a quadrupole mass spectrometer (Q-MS). The addition of TCP prolonged the induction period for decomposition of the lubricant. During the friction processes, hydrogen and gaseous hydrocarbons desorbed as tribochemical reaction products. XPS analysis revealed that the tribofilm from the additive was mainly composed of iron phosphate, which decreased the probability of generating a nascent surface, resulting in the reduction of desorption rate of gaseous products. The critical load for the mechanical activation of the decomposition correspondingly doubled.     

Structural characteristics and mechanism of action of antioxidant anticorrosive additives for perfluoropolyalkylether fluids

The combination energies of perfluoropolyalkyletherphenylamide (PFPEA) with perfluoropolyalkylether oxygen radicals (R_fO) and with Fe atoms have been calculated by quantum chemical methods. The values are ‐417.33 and ‐105.02 kJ/mol, respectively. The structural characteristics and the mechanism of action of an antioxidant anticorrosive additive have been explored. It was found that the highest occupied molecular orbital (HOMO) of the additive is a π molecular orbital and it has the properties of a typical electron donor. The HOMO of the PFPEA additive reacts with the lowest unoccupied molecular orbital (LUMO) of an Fe atom and forms a coordinate bond and chemically adsorbed film on the metal surface. The film inhibits catalytic degradation and protects the metal surface. The additive is also capable of accepting the electron of R_fO. The R_fO radical combines automatically with the C₇ atom of the benzene ring to terminate the R_fO decomposition reaction. The PFPEA additive has been synthesized and analysed by UV and IR. Measurement of antioxidant anticorrosive properties indicates that, in the presence of the synthesised additive, the weight loss of a perfluoropolyether lubricant is reduced by about 7 times and the degradation temperature is increased by about 19°C compared with the base oil without the additive. The experimental results are consistent with the conclusions from the theoretical study.     

The Effect of Phosphazene additives to passivate and stabilize lubricants at the head/disk interface

There have been a number of applications for lubricant additives in the disk drive media area, the first of which was for pseudo-contact recording with inductive heads (tri-pad sliders) in an effort to stabilize the head/disk interface and minimize lube decomposition under hot/wet conditions. A number of additives have been tried which include antioxidants as well as Lewis bases, the latter in an effort to passivate the catalytic activity of the Lewis Acid sites on the slider which results in the decomposition of the perfluoropolyether (PFPE) lubricants such as Z-Dol, AM and Z-Tetraol. In addition to this passivation action of the phosphazene toward catalytic decomposition of the lubricant, it has recently been reported that the use of X-1P (a cyclic phosphazene) also enhances reflow of the lube, increasing the durability of the head disk interface. In this regard there are still a number of unanswered questions that pertain to the mechanism of the interaction of the X-1P with the lubricant and/or carbon to cause this increase in mobility of the lubricant resulting in the enhanced durability.There are numerous technical issues associated with the use of the various additives with the main one being compatibility between the additive and the PFPEs as well as the carbon surfaces on which they are coated. These issues include bonding, phase separation of the components, and the transfer mechanism for the additive to the slider where the passivation is required.In this paper, we will look at the interaction of the X-1P with the carbon overcoat on the media in an effort to try to better understand the mechanism of such an interaction and its effect on the mobility of the lubricant as well as the amount of bonded lube on the disks.     

Computational Chemistry of Soluble Additives for Perfluoropolyalkylether Liquid Lubricants

Computational chemistry has been applied in a practical manner to a perfluoropolyalkylether (PFPAE) liquid lubricant research and development program. Additives have been previously shown to be effective in a PFPAE liquid lubricant candidate gas turbine engine oil base fluid as oxidation inhibitors/metal deactivators, lubricity additives and antirust additives. In this effort, low energy configuration computer models of the base fluid and of selected additives were created. Simulated docking of the additive molecules in the base fluid media, onto low carbon steel and onto iron oxide substrates, provided information on the strength of the substrate/additive interactions. Also, the visual representation of each additive molecule's alignment on the metallic surface has provided insight into selection of the optimnum functionality in designing new additives. Data on the additive/metal attraction and corresponding additive effectiveness are presented.     

A Theoretical Study of Vapor Lubrication for Heat Assisted Magnetic Recording

Heat assisted magnetic recording (HAMR) is a promising technique to overcome the superparamagnetic limit to further increase the areal recording density of hard disk drives. However, HAMR brings about serious problems to the slider-disk interface, such as lubricant depletion on disk surface caused by laser heating. It is proposed to overcome the lubricant depletion problem by using vapor lubrication. The lubricant film formation process on disk surface in vapor lubrication is studied theoretically based on fundamental adsorption and desorption theories. The controlling parameters of lubricant film thickness and film formation time are identified. It is found that the lubricant film thickness is controlled mainly by lubricant vapor pressure and molecular weight. The film formation time can be shortened by using low molecular weight lubricant and high temperature lubricant vapor.     

Lubricant and additive effects on spur gear fatigue life

Spur gear endurance tests were conducted with six lubricants using a single batch of consumable-electrode vacuum melted (CVM) AISI 9310 spur gears. The sixth lubricant was divided further into four batches, each of which had a different additive content. Lubricants tested with a phosphorus-type load carrying additive showed a statistically significant improvement in life over lubricants without this type of additive. The presence of sulphur-type antiwear additives in the lubricant did not appear to affect the surface fatigue life of the gears. No statistical difference in life was produced with those lubricants of different base stocks but with similar viscosity, pressure-viscosity coefficients and antiwear additives. Gears tested with a 0.1 wt % sulphur and 0.1 wt % phosphorus EP additives in the lubricant had reactive films that were 200 to 400 Å (0.8 to 1.6 μin) thick.