Lubrication Mechanism of Phosphonium Phosphate Ionic Liquid Additive in Alkylborane–Imidazole Complexes

The assessment of ionic liquids (ILs) as lubricants in several tribological systems has shown their ability to provide remarkable reduced friction and protection against wear, whether they are used as additives or in the neat form. However, their corrosion and limited solubility in non-polar hydrocarbon oils represent the bottleneck-limiting factors for the use of ILs as lubricants. Therefore, in order to tackle these problems, mixtures of alkylborane–imidazole complexes with one halogen-free IL as additive were used in this study. The knowledge of the additive–surface interactions and hence the understanding of tribological properties are an important issue for lubricant formulations and were also investigated in this work. Thus, combination effects between two ionic liquid additives, a halogenated and a halogen-free one, were evaluated by a ball-on-disc-type tribometer under boundary lubrication conditions. Effective friction reduction and anti-wear properties have been demonstrated in tribological investigations when adding between 0.7 and 3.4 wt% of the halogen-free IL into base fluid composed of alkylborane–imidazole complexes. X-ray photoelectron spectroscopy analyses of the steel specimens were conducted to study the correlation between tribological properties and chemical surface composition of the boundary films formed on the rubbing surface. This work suggests potential applications for using halogen-free ILs as additives for synthetic ionic liquid lubricants.     

Nanotribological properties of novel lubricants for magnetic tapes

Two classes of novel lubricants, perfluoropolyethers (PFPE) and ionic liquids (ILs), were deposited on metal film magnetic tapes. The adhesive force and coefficient of friction of lubricated and unlubricated tapes were investigated at the nanoscale with an atomic force microscope (AFM) as a function of various humidity and temperature conditions. Microscale tests with a ball-on-flat tribometer were also performed in order to study the length-scale effects on friction. Wear at ultralow loads was simulated and the lubricant removal mechanism was investigated by monitoring the friction force, surface potential and contact resistance with the AFM. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) experiments were conducted to determine the chemical species that affect intermolecular bonding and as an aid in interpreting how the lubricant film tribological properties vary with the environmental conditions. Z-TETRAOL, one of the PFPEs, was found to exhibit the lowest adhesion and friction among the lubricant films studied. The ionic liquid 1,1′-(pentane-1,5-diyl)bis(3-hydroxyethyl-1H-imidazolium-1-yl) di[bis(trifluoromethanesulfonyl)imide)] exhibited comparable nanotribological properties with the PFPEs. This is attributed to the presence of hydroxyl groups at its chain ends, which can hydrogen bond with the surface similar to PFPEs.     

Nanotribological characterization of molecularly thick lubricant films for applications to MEMS/NEMS by AFM

Molecularly thick perfluoropolyether (PFPE) films are considered to be good protective films for micro/nanoelectromechanical systems (MEMS/NEMS) to reduce stiction, friction, and improve their durability. Understanding the nanotribological performance and mechanisms of these films are quite important for efficient lubrication for MEMS/NEMS devices. These devices are used in various operating environments and their effect on friction, adhesion and durability needs to be clarified. For this purpose, mobile and chemically bonded PFPE films were deposited by dip coating technique. The friction and adhesion properties of these films were characterized by atomic force microscopy (AFM). The effect of rest time, velocity, relative humidity, and temperature on nanotribological properties of these films was studied. Durability of these films was also measured by repeated cycling tests. The adhesion, friction mechanisms of PFPE at molecular scale, and the mechanisms of the effect of operating environment and durability are subject of this paper. This study found that adsorption of water, formation of meniscus and its change during sliding, viscosity, and surface chemistry properties play a big role on the friction, adhesion, and durability of the lubricant films.     

Tribological Performance and Mechanism of Phosphate Ionic Liquids as Additives in Three Base Oils for Steel-on-aluminum Contact

Butylammonium dibutylphosphate and tetrabutylammonium dibutylphosphate ionic liquids (ILs) were evaluated as antiwear additives for steel-on-aluminum contact in three different base oils, a polyalphaolefin, an ester oil and an IL 1-methy-3-hexylimidazolium hexafluorophosphate, respectively, with similar viscosity and different polarities. The friction experiments were carried out on an Optimal SRV-IV oscillating reciprocating friction and wear tester at room temperature. Results indicate phosphate ILs can effectively improve the tribological properties of the base oil, especially the antiwear property, as additives for steel/aluminum contacts. For the base oils PAO10 and PAO40 with different viscosities, the higher viscosity of PAO40 can be beneficial to reducing the friction coefficient. The worn surface morphologies and chemical compositions of wear scars were analyzed by a JSM-5600LV scanning electron microscope and PHI-5702 multifunctional X-ray photoelectron spectrometer (XPS). The XPS analysis results illustrate that the phosphate IL additives in the base oils with different polarities exhibit the same tribological mechanism. A synergy exists between the adsorbed layers and boundary-lubricating films generated from the tribochemical reaction of IL and the substrate surface, which may reduce the friction coefficient and wear volume of the friction pairs.     

Nanotribological Behavior of Ultra-thin Al2O3 Films Prepared by Atomic Layer Deposition

Si-based nano/micro-electromechanical system (NEMS/MEMS) devices with contacting and rubbing structures cannot run reliably due to their poor tribological performance. A thin alumina (Al₂O₃) film is a promising candidate for the protective coating in the applications of NEMS/MEMS devices. In this study, nanotribological behavior of ultra-thin Al₂O₃ films prepared by atomic layer deposition on a Si (100) substrate was investigated in comparison with that of Si (100). X-ray photoelectron spectroscopy was used to determine the composition of Al₂O₃ films. Atomic force microscopy with different tips was employed to measure the scratch resistance, adhesion and friction forces of various samples. The results show that Al₂O₃ films have larger scratch resistance than that of Si (100). In addition, the adhesion and friction forces of Al₂O₃ films are smaller than that of Si (100). Thus, the Al₂O₃ films are capable of a wide application in Si-based NEMS/MEMS devices. The improved tribological performance of Al₂O₃ films is attributed to their hydrophobic properties.     

Study of the Conductivity and Tribological Performance of Ionic Liquid and Lithium Greases

Ionic liquid (IL) lubricating greases were prepared using 1-hexyl-3-methylimidazolium tetrafluoroborate and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide as base oil and polytetrafluoroethylene (PTFE) as thickener, respectively. Three kinds of lithium greases were also prepared using lithium ILs ([Li(PAG)]X) as base oil and PTFE as thickener. 1-Ethyl-3-methyl imidazolium hexafluorophosphate as an additive was added to the PAG grease, which was prepared using polyalkylene glycol monobutyl ether (PAG) as base oil and PTFE as thickener. The conductivities and tribological properties of the prepared lubricating greases were investigated in detail. Scanning electron microscopy and X-ray photoelectron spectroscopy were employed to explore the friction and wear mechanism. The results showed that the IL and lithium lubricating greases have conductivities and excellent tribological properties. Especially, IL greases have the highest conductivity. The excellent tribological properties are attributed to the formation of boundary films consisting of both tribo-chemical reaction films and physical absorption films, while high conductivities are attributed to the intrinsic electric fields of the ILs.     

Effect of the Anion on the Tribological Properties of Ionic Liquid Nano-Films on Surface-Modified Silicon Wafers

The films of three kinds of 3-butyl-1-methylimidazolium base ionic liquids with thickness of 2 nm were prepared on hydroxyl-terminated and amino-terminated Si substrates by dip-coating method. As anions, tetrafluoroborate, hexafluorophosphate, and adipate, respectively, were chosen. The tribological performances of these thin films were examined by the determination of the film durability and friction coefficient by means of a UMT-2MT tribometer using a steel ball as counterpart. The morphologies of worn surfaces were investigated by a non-contact interferometric microscope. The findings showed that 3-butyl-1-methyl-imidazolium hexafluorophosphate having the poorest hydrophilicity of the ionic liquids exhibited the best tribological properties on aminated Si surface at 0.4 N and 4 Hz.     

Tribological properties of ultra-thin ionic liquid films on single-crystal silicon wafers with functionalized surfaces

Two kinds of room temperature ionic liquid (RTIL) films carrying vinyl and hydroxyl functional groups were prepared on single-crystal Si wafers by spin coating. The tribological properties of the RTIL films sliding against AISI-52100 steel ball and Si₃N₄ ball in a ball-on-plate configuration were investigated on a dynamic–static friction coefficient measurement apparatus, using perfluoropolyether (PFPE) film as a comparison. The tribological behaviors of the ionic liquid films sliding against the same counterparts at extended test durations were also evaluated using a universal UMT-2MT test rig. The morphologies of the wear tracks of the RTIL films and the counterparts were examined using a scanning electron microscope equipped with an energy-dispersive X-ray analyzer attachment. It was found that the tribological performances of the ionic liquid films were closely related to the chemical structures of the RTILs and the chemical characteristics of the substrate surfaces. The films of vinyl group functionalized ionic liquids on hydroxylated substrate and vinyl group modified substrate exhibited very good friction-reduction and wear-resistant properties. It was assumed that there were enough strong forces between the films and substrate in these cases, and the ionic liquid molecules maintained good flexibility simultaneously. The films on hydrogen-terminated and methyl-terminated substrate showed poor tribological performance, which could be related to the relatively weak forces between the films and substrates. Moreover, the films on hydroxylated substrate showed lower friction at higher sliding velocities, which was assumed to be governed by the more rapid adsorption of the ionic liquid molecules on the steel ball at a higher sliding velocity. In addition, the ionic liquid films also had excellent tribological properties as they slid against silicon nitride ball. Therefore, it was supposed that the ionic liquid films could be used as a kind of universal lubricant for various combinations of the frictional pair.     

Fabrication of ionic liquid thin film by nano-inkjet printing method using atomic force microscope cantilever tip

We demonstrate the fabrication of thin films of ionic liquid (IL), 1-butyl-3-methyl-imidazolium tetrafluoborate, by nano-inkjet printing method using an atomic force microscope (AFM) cantilever. The IL filled in a pyramidal hollow of the AFM cantilever tip was extracted from an aperture at the bottom of the hollow and deposited onto a Pt substrate when the bias voltage was applied between the cantilever and the substrate. We succeeded in fabricating IL thin films with a thickness of 4 nm. The areas and thicknesses of IL thin films were controlled by the fabrication conditions in this method, which is also useful for the investigations of nanometer-scale properties of ionic liquid.     

Preparation of functional ionic liquids and tribological investigation of their ultra-thin films

Novel ionic liquid materials based on 1-alkyl-4-[5-(alkylsulfanyl)-1,3,4-oxadiazol-2-yl] pyridinium tetrafluoroborate derivatives were synthesized. Ultra-thin ionic liquid films were prepared on silicon wafers by means of spin-coating and their tribological properties were investigated. The wear life increases when the chain length decreases. Under low load, they show good tribological properties which are closely related to the interaction between ionic liquid and substrate surface, especially the film of 1-ethyl-4-[5-(ethylsulfanyl)-1,3,4-oxadiazol-2-yl] pyridinium tetrafluoroborate, it has low friction coefficient and long wear life. So, this kind of ionic liquid can be potentially applied as ultra-thin lubricating coating.     

Investigation of the Stability and Tribological Performance of Ionic Nanoliquids

In previous studies, nanoparticles and ionic liquids (ILs) have been used separately as oil additives and have been shown to reduce friction and wear. In this study, the stability and tribological performance of ionic nanoliquids (INLs), which combine nanoparticles and miscible ionic liquids together as oil additives, were investigated. Zinc oxide nanoparticles were dispersed in a mixture of polyalphaolefin (PAO) oil and ionic liquid (tetradecyltrihexylphosphonium bis (2,4,4-trimethylpentyl phosphinate)) using an ultrasonic homogenizer. The coefficient of friction was studied using a tribometer with a ball-on-disk configuration. The wear track was measured using a Bruker Contour GT-K Optical Profiler and the wear volume was calculated. The effects of concentration and load on the coefficient of friction and wear were investigated. The effects of ultrasonic mixing time and nanoparticle concentration on the stability of the solutions were also studied.     

Tribological properties of alkyl and hydroxyl groups on the imidazolium tetrafluoroborate ionic liquids

We present an investigation of effect of alkyl chain length and hydroxyl group functionalisation on the tribological properties of imidazolium tetrafluoroborate ionic liquids. Four kinds of hydroxyl‐functionalised ionic liquids with the alkyl chain of C₁–C₁₀ were synthesised, and the relationships between their structure and physicochemical properties such as viscosity, thermal stability and corrosion, before and after incorporation of a hydroxyl group, were measured. In particular, the studies on their lubrication properties as ionic liquid (IL) lubricants for steel–steel contacts, including the friction coefficient, the wear volume and so on, were particularly emphasised. Moreover, an in‐depth exploration about the function mechanism and failure mode of the ILs during the friction process were studied using the scanning electron microscope and X‐ray photoelectron spectroscope technologies, and a proposed interaction model between ILs and steel substrate was presented. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterization and tribological investigation of self-assembled lanthanum-based thin films on glass substrates

Rare-earth (RE) (lanthanum-based) thin films were prepared on hydroxylated glass substrates by a self-assembling process from specially formulated solution. Atomic force microscope (AFM) and X-ray photoelectron spectrometry (XPS) and scanning electron microscope (SEM) are used to characterize the thin films. The tribological properties of the as-prepared thin films sliding against a steel ball were evaluated on a friction and wear tester. The tribological experiment shows that the friction coefficient of glass substrate reduced from 0.85 to 0.13 after the formation of RE self-assembled film (SAM) on its surface. And the RE self-assembled film has longer wear life (2880 sliding pass). It is demonstrated that RE self-assembled film exhibited good wear resistant property. The superior friction reduction and wear life of RE films are attributed to good adhesion of the film to the substrate and special characteristic of the RE elements.     

Microtribological behaviour of thin DLC films using different testing methods

To enhance the lifetime and reliability of microcomponents, thin microtribological films are applied to microparts. With reduction of the component size, investigation methods for tribological testing must be adapted. This paper studies the microtribological behaviour of thin diamond‐like carbon (DLC) films using different testing methods. To tie in with macroscopic results, to determine friction we used the well‐known pin‐on‐disc test with spherical surfaces of 10 mm diameter under a typical load of 3 N. For investigations of the behaviour under single asperity contact, Atomic Force Microscope (AFM) methods with applied loads of a few hundred micronewtons were used. Investigations on thin DLC films showed that the friction coefficient under single asperity contact is strongly dependent on the applied load and the resulting contact area. Especially for thin films (up to a few hundred nanometres) the friction coefficient is influenced by the substrate material. With decreasing substrate Young's modulus the friction coefficient also decreases. On the other hand, an increase in the abrasive wear resistance was observed using soft substrate materials. In this paper we show that the friction coefficient was also reduced by a simple surface structure. For investigations we used photolithography to create concentric circles in different substrates. This resulted in a behaviour like riding on rails for the pin‐on‐disc test. Depending on the tribological pairing the friction coefficient was reduced to more than 50% of the original value. Copyright © 2006 John Wiley & Sons, Ltd.     

The Influences of Methyl Group at C2 Position in Imidazolium Ring on Tribological Properties

Tribological properties of two kinds of imidazolium ionic liquids (ILs) of 1,2-dimethyl-3-hexylimidazolium bis(trifluoromethylsulfonyl)imide (L-F116) and 1-dimethyl-3-hexylimidazolium bis(trifluoromethylsulfonyl)imide (L-F106) were evaluated as lubricant additives in poly(ethylene glycol) (PEG) for the steel–steel sliding pair by using an Optimol-SRV oscillating friction and wear test at the room temperature. At the same time, their electrochemical corrosion behaviors were measured by Tafel polarization. The morphologies of the worn surfaces were observed using a scanning electron microscope (SEM). The chemical states of several typical elements on the worn surfaces were examined by means of X-ray photoelectron spectroscopy (XPS). The results show that corrosion phenomena of PEG containing ILs on pure copper are negligible compared to PEG at room temperature. The 2-substituted imidazolium IL L-F116 shows excellent tribological performance and is superior to L-F106 in terms of anti-wear performance and load-carrying capacity. The worn surfaces were characterized to have slight abrasion and the XPS results indicated the formation of tribochemical adsorption and chemical reaction films on the worn surfaces.     

Imidazolium hexafluorophosphate ionic liquids as high temperature lubricants for steel–steel contacts

A series of long-chain 1,3-dialkyl imidazolium ionic liquids (ILs) were synthesized and evaluated as lubricants for steel–steel contacts both at room temperature and 150 °C. Relationship between the alkyl chain length and the tribological properties of the ILs was investigated in detail. The results indicated that the ILs bearing long alkyl side chains have excellent friction-reducing and anti-wear properties, especially at high temperatures and high loads. The worn surfaces of steel discs were observed and analyzed by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The friction reduction and load carrying capacity were supposed to be due to the formation of high quality boundary films consisting of both tribochemical reaction film and the ordered absorption film.     

MoSx/MoSx-Mo纳米多层膜的制备及其环境摩擦学特性

用直流磁控溅射在钢基体上交替溅射制备了MoSx/MoSx-Mo纳米多层膜。采用划痕仪测试薄膜与基体的结合力;采用SEM和XRD分析了纳米多层膜的形貌和显微结构;在球-盘式微摩擦试验机上测试了纳米多层膜在真空和潮湿空气中的摩擦学性能。结果表明,纳米多层膜的结合力优于纯MoS2膜。随着溅射沉积气压的升高,MoSx(002)面择优取向减弱,纳米多层膜的结合力下降。溅射气压0.24 Pa沉积的纳米多层膜在真空和潮湿空气中都呈现出最低的摩擦因数和磨损率,具有优异的环境摩擦磨损特性。     

Tribological properties of self-assembled monolayers on Au,SiOx and Si surfaces

Using interfacial force microscopy (IFM), the tribological properties of self-assembled monolayers (SAM) on Si surfaces produced by a new chemical strategy are investigated and compared to those of “classical” SAM systems, which include alkanethiols on Au and alkylsilanes on SiO_x. The new SAM films are prepared by depositing n-alkyl chains with OH-terminations onto Cl-terminated Si substrates. The chemical nature of the actual lubricating molecules, n-dodecyl, is kept constant in all three thin film systems for direct comparison and similarities and differences in tribological properties are observed. The adhesion strength is virtually identical for all three systems; however, frictional properties differ due to differences in film packing. Differences in the chemical bonds that attach the lubricant molecules to the substrate are also discussed as they influence variations in film wear and durability. It is demonstrated that the new SAM films are capable of controlling the friction and adhesion of Si surfaces equally well as the classical SAMs and are potentially more reproducible and more durable.     

类金刚石薄膜微观摩擦性能的FFM评价——针尖尺度效应

采用等离子体增强气相沉积制备了类金刚石薄膜，利用原子力显微镜的轻敲模式观察了它们的形貌，并在考虑外加载荷和扫描速度的基础上，用摩擦力显微镜（FFM）对比考察了尖端探针和平头探针对类金刚石薄膜摩擦性能评价的影响。结果表明：类金刚石薄膜的表面粗糙度随基底负偏压的增加而减小；存在于探针和类金刚石薄膜之间的水膜对尖端探针的剪切阻力贡献较大，且尖端探针测得的摩擦力变化趋势受扫描速度影响显著；水膜对平头探针起着不同形式的润滑作用，从而导致平头探针和类金刚石薄膜之间摩擦性能的速度效应存在差异；利用摩擦力显微镜考察类金刚石薄膜的摩擦性能时，存在着明显的针尖尺寸效应。     

Tribological Characteristics of Alkylimidazolium Diethyl Phosphates Ionic Liquids as Lubricants for Steel–Steel Contact

Tribological properties of three novel phosphates-based ionic liquids (ILs), i.e., 1,3-diethyl imidazolium diethylphosphate, 1-ethyl-3-butyl imidazolium diethylphosphate, and 1-ethyl-3-octyl imidazolium diethylphosphate, were evaluated as lubricants for the steel–steel sliding pair by using an Optimol-SRV oscillating friction and wear tester. The chemical compositions of the boundary films generated on steel contact surfaces were analyzed with the use of a scanning electron microscope (SEM) with a Kevex energy dispersive X-ray analyzer attachment (EDS), and an X-ray photoelectron spectrometer (XPS). The results showed that these phosphate functional group-containing ionic liquids exhibit excellent tribological performance especially at a moderate temperature. The imidazole phosphate ionic liquid has no corrosion to steel. The mechanism for the friction-reduction and anti-wear effect of ionic liquids has also been proposed and discussed from the tribochemistry point of view.