Multi-environmental lubrication performance and lubrication mechanism of MoS2/Sb2O3/C composite films

MoS₂–Sb₂O₃–C composite films exhibit adaptive behavior, where surface chemistry changes with environment to maintain the good friction and wear characteristics. In previous work on nanocomposite coatings grown by PVD, this type of material was called a “chameleon” coating. Coatings used in this report were applied by burnishing mixed powders of MoS₂, Sb₂O₃ and graphite. The solid lubricant MoS₂ and graphite were selected to lubricate over a wide and complementary range including vacuum, dry air and humid air. Sb₂O₃ was used as a dopant because it acts synergistically with MoS₂, improving friction and wear properties. The MoS₂–Sb₂O₃–C composite films showed lower friction and longer wear life than either single component MoS₂ or C film in humid air. Very or even super low friction and long wear-life were observed in dry nitrogen and vacuum. The excellent tribological performance was verified and repeated in cycles between humid air and dry nitrogen. The formation of tribo-films at rubbing contacts was studied to identify the lubricating chemistry and microstructure, which varied with environmental conditions. Micro-Raman spectroscopy and Auger electron spectroscopy (AES) were used to determine surface chemistry, while scanning electron microscopy and transmission electron microscopy were used for microstructural analysis. The tribological improvement and lubrication mechanism of MoS₂–Sb₂O₃–C composite films were caused by enrichment of the active lubricant at the contact surface, alignment of the crystal orientation of the lubricant grains, and enrichment of the non lubricant materials below the surface. Sb₂O₃, which is not lubricious, was covered by the active lubricants (MoS₂ – dry, C – humid air). Clearly, the dynamics of friction during environmental cycling cleaned some Sb₂O₃ particles of one lubricant and coated it with the active lubricant for the specific environment. Mechanisms of lubrication and the role of the different materials will be discussed.     

Wear of single crystal silicon as a function of surface roughness

With increasing activities on micro electro-mechanical systems (MEMS) type microactuators, there is a growing need in understanding the tribological properties of silicon, the most commonly used wafer material for those devices. In particular, it is of interest if single crystal silicon used in microactuators exposed to rather low vertical loads is subject to wear. Therefore, wear tests using monocrystalline silicon on both sides of the tribological interface were conducted.A classic way to measure wear on sliders in contact with a tape or a rotating disk is to create an imprint using a Berkovich diamond tip mounted on a picoindenter. However, in our case we used a different approach. We created three studs on a slider’s surface by recessing the material outside the studs through an ion milling process. During the wear tests, the studs wore off. By measuring the remaining stud height, the wear volume could be determined at any point in time. The tests were performed on a pin on disk tester with a gimbaled slider to realize a flat on flat contact and a rather low normal force of 30 mN.     

Rippling on Wear Scar Surfaces of Nanocrystalline Diamond Films After Reciprocating Sliding Against Ceramic Balls

The formation of nanoscopic ripple patterns on top of material surfaces has been reported for different materials and processes, such as sliding against polymers, high-force scanning in atomic force microscopy (AFM), and surface treatment by ion beam sputtering. In this work, we show that such periodic ripples can also be obtained in prolonged reciprocating sliding against nanocrystalline diamond (NCD) films. NCD films with a thickness of 0.8 µm were grown on top of silicon wafer substrates by hot-filament chemical vapor deposition using a mixture of methane and hydrogen. The chemical structure, surface morphology, and surface wear were characterized by Raman spectroscopy, scanning electron microscopy (SEM), and AFM. The tribological properties of the NCD films were evaluated by reciprocating sliding tests against Al₂O₃, Si₃N₄, and ZrO₂ counter balls. Independent of the counter body material, clear ripple patterns with typical heights of about 30 nm induced during the sliding test are observed by means of AFM and SEM on the NCD wear scar surfaces. Although the underlying mechanisms of ripple formation are not yet fully understood, these surface corrugations could be attributed to the different wear phenomena, including a stress-induced micro-fracture and plastic deformation, a surface smoothening, and a surface rehybridization from diamond bonding to an sp ² configuration. The similarity between ripples observed in the present study and ripples reported after repeated AFM tip scanning indicates that ripple formation is a rather universal phenomenon occurring in moving tribological contacts of different materials.     

Nanotribology and lubrication mechanisms of inorganic fullerene-like MoS<Subscript>2</Subscript> nanoparticles investigated using lateral force microscopy (LFM)

Inorganic fullerene-like (IF) MoS₂ nanoparticles were produced by arc discharge in water, and their tribological properties were investigated using a lateral force microscope in dry nitrogen and humid air. Two types of tips – Si and Si₃N₄ tips were used in this work. The sharp Si tip produced a much higher contact stress than the blunt Si₃N₄ tip. The measurement of lateral forces using a Si₃N₄ tip resulted in almost no wear, while the measurement made using a Si tip resulted in MoS₂ transfer due to the high contact stress. For comparison, measurements were also made on MoS₂ films grown by pulsed laser deposition (PLD). The experimental results demonstrated that IF-MoS₂ nanoparticles had significantly lower friction than the MoS₂ films prepared by PLD. Variation of the test environment from dry to wet did not affect the tribological performance of the IF material as much as it did PLD films due to the chemical inert structure of the IF-MoS₂ nanoparticles. The multi-wall-encapsulated structure of inorganic fullerenes has a nearly isotropic geometry. They can supply a slippery surface in all orientations, though only the basal planes of 2H–MoS₂ crystals are optimum for lubrication. Therefore, the inorganic fullerenes do not have to be oriented by rubbing as does most layer-structured solid lubricants. However, the lack of reactive edge planes impedes bonding of the lubricant to the surface. The lubrication mechanisms of IF-MoS₂ nanoparticles are discussed in detail.     

Near-Edge X-ray Absorption Fine Structure Imaging of Spherical and Flat Counterfaces of Ultrananocrystalline Diamond Tribological Contacts: A Correlation of Surface Chemistry and Friction

A recently installed synchrotron radiation near-edge X-ray absorption fine structure (NEXAFS) full field imaging electron spectrometer was used to spatially resolve the chemical changes of both counterfaces from an ultra- nanocrystalline diamond (UNCD) tribological contact. A silicon flat and Si₃N₄ sphere were both coated with UNCD, and employed to form two wear tracks on the flat in a linear reciprocating tribometer. The first wear track was produced using a new, unconditioned sphere whose surface was thus conditioned during this first experiment. This led to faster run-in and lower friction when producing a second wear track using the conditioned sphere. The large depth of field of the magnetically guided NEXAFS imaging detector enabled rapid, large area spectromicroscopic imaging of both the spherical and flat surfaces. Laterally resolved NEXAFS data from the tribological contact area revealed that both substrates had an as-grown surface layer that contained a higher fraction of sp ²-bonded carbon and oxygen which was mechanically removed. Unlike the flat, the film on the sphere showed evidence of having graphitic character, both before and after sliding. These results show that the graphitic character of the sphere is not solely responsible for low friction and short run-in. Rather, conditioning the sphere, likely by removing asperities and passivating dangling bonds, leads to lower friction with less chemical modification of the substrate in subsequent tests. The new NEXAFS imaging spectroscopy detector enabled a more complete understanding of the tribological phenomena by imaging, for the first time, the surface chemistry of the spherical counterface which had been in continual contact during wear track formation.     

Nano-wear of the diamond AFM probing tip under scratching of silicon, studied by AFM

In order to improve such a widely used microtribological testing procedure as surface scratching by an AFM diamond tip, an experimental study has been carried out using single-crystalline silicon as the tested material. Wear of the AFM diamond tip under scratching was observed by a decrease in the scratch depth with increasing wear cycles and by the direct imaging of the diamond tip shape using a Si₃N₄ AFM tip. It was shown that the current widely used experimental method, which assumes the diamond tip to be non-wearable, introduces uncontrollable error into the obtained values for the tested material's wear rate. The harder the tested material, the larger may be the tip wear, and, therefore, the bigger may be its effect on the obtained wear rate values. The specific wear rates for the diamond tip and a silicon wafer were estimated to be 1.4 × 10^-9 and 4.5 × 10^-4 mm³/(N m), respectively.     

Relating Molecular Structure to Tribological Chemistry: Borate Esters on Copper

The surface and tribological chemistry of 2-propanol and borate esters, isopropoxy tetramethyl dioxaborolane (ITDB), and tetramethyl dioxaborolane (TDB) as gas-phase lubricants for copper surfaces are compared by measuring the friction coefficient and contact resistance in an ultrahigh vacuum tribometer. 2-propanol reacts on copper below room temperature to desorb primarily acetone and causes no friction reduction when used as a gas-phase lubricant. TDB decomposes to deposit BO_x species on the surface and produces an initial decrease in friction coefficient that is not sustained. ITDB, which reacts at room temperature to form a tetramethyl dioxaborolide species on the surface, results in an immediate and sustained decrease in friction coefficient when used as a gas-phase lubricant for copper. This indicates that the surface chemistry of the borate esters can be correlated with their tribological properties and illustrates the effect of replacing a hydrogen atom in TDB with a 2-propoxy group in ITDB on both the surface and tribological chemistry. Analysis of the species formed in the wear track after lubrication with ITDB reveals the presence of graphitic or diamond-like carbon and oxygen, and these elements are also found in the subsurface region of the sample. Rubbing the sample in vacuo after reacting with ITDB shows the removal of a boundary film where the coefficient remains constant and the subsequent removal of the subsurface layer in which the contact resistance rises to its original value.     

Surface force microscope observations of corrosive tribological wear on single crystal NaNO3 exposed to moist air

Simultaneous tribological loading and exposure to a chemically reactive environment can yield wear processes not produced by either stimulus alone. We report surface force microscopic (SFM) observations of cleaved, single crystal NaNO₃ in air, where tribological loading was provided by the SFM tip itself and chemical exposure was due to controlled introduction of water vapor at relative humidities from 10 to 65%. Scanning in the contact mode with nN loads at 30–50% relative humidity produces readily visible surface modifications, including preferential removal of material along steps. Material transfer along the surface can yield parallel ridges and depressions tens of nanometer high. In contrast, scanning in the tapping mode under certain humidity conditions produces localized deposition, possibly reflecting the dehydration of solvated ions and subsequent incorporation into the solid phase. We discuss the influence of contact force, tip velocity, relative humidity, and possible mechanochemistry on the rates of wear and deposition.Department of Mechanical Engineering, Kansai University, Osaka 564, Japan.     

Friction and wear of diamondlike carbon on fine-graindiamond

Friction and wear behavior of ion-beam-deposited diamondlikecarbon (DLC) films coated on chemical-vapor-deposited (CVD),fine-grain diamond coatings were examined in ultrahigh vacuum,dry nitrogen, and humid air environments. The DLC films wereproduced by the direct impact of an ion beam (composed of a 3 :17 mixture of Ar and CH₄) at ion energies of 1500 and700 eV. Sliding friction experiments were conducted withhemispherical CVD diamond pins sliding on four differentcarbon-base coating systems: DLC films on CVD diamond; DLC filmson silicon; as-deposited, fine-grain CVD diamond; andcarbon-ion-implanted, fine-grain CVD diamond on silicon. Resultsindicate that in ultrahigh vacuum theion-beam-deposited DLC films on fine-grain CVD diamond (similarto the ion-implanted CVD diamond) greatly decrease both thefriction and wear of fine-grain CVD diamond films and providesolid lubrication. In dry nitrogen and in humid air,ion-beam-deposited DLC films on fine-grain CVD diamond films alsohad a lowsteady-state coefficient of friction and a low wear rate. Thesetribological performance benefits, coupled with a wider range ofcoating thicknesses, led to longer endurance life and improvedwear resistance for the DLC deposited on fine-grain CVD diamondin comparison to the ion-implanted diamond films. Thus, DLCdeposited on fine-grain CVD diamond films can be an effectivewear-resistant, lubricating coating regardless of environment.     

Effect of surface chemistry on the tribological performance of a MEMS electrostatic lateral output motor

The effect of surface chemistry on the tribological performance and reliability of a MEMS lateral output motor is reported. Relative humidity (RH) and octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) coatings were used to change surface chemistry. Electrical and tribological performance of uncoated and OTS-coated motors were found to be dependent on RH. For uncoated motors, excessive wear of sliding contacts and welding (permanent adhesion) of static contacts were observed at 0.1% RH. Degradation of electrostatic force and high static friction (stiction) forces limited dynamic performance and reliability and caused device sticking at and above 70% RH. Around 50% RH, uncoated motors exhibited negligible wear, low adhesion, and a wear life at least three orders of magnitude longer than in the dry environment (experiments were stopped without failure after about one billion cycles). Water vapor behaved as a gas phase replenishable lubricant by providing a protective adsorbed film. The OTS coating broadened the operating envelope to 30–50% RH and reduced stiction, which allowed better dynamic performance at high RH. The OTS coating improved durability at 0.1% RH, but it was still poor. At high RH, stiction problems reoccurred when the OTS coating was worn away. By controlling and balancing surface chemistry (adsorbed water and OTS), excellent performance, low friction and wear, and excellent durability were attained with the lateral output motor.     

The wear rate of n-type Si(100)

Single-crystal Si(100) (n type) was scratched at room temperature by a single-point 90° pyramidal diamond in each of the following fluids: reagent-grade absolute ethanol, methanol, acetone and deionized water. The wear rate in each case was determined from a measurement of the cross-sectional areas of circular multiscratch grooves and the increase in this area with scratching time. These areas vary as the contact force on the diamond and the fluid covering the silicon surface during the scratching test vary. As expected, the wear rate depended on the force (dead-weight load) on the diamond (the wear rate increased as the force was increased) but fluids also had a significant effect on the wear. The wear rate of silicon scratched in ethanol is twice that in deionized water when the dead-weight load on the diamond is 0.49 N and all other experimental variables are held constant. These results were compared with two models of abrasive wear of ceramic materials.     

Influence of humidity on microtribology of vertically aligned carbon nanotube film

The aim of this study is to probe the influence of water vapor environment on the microtribological properties of a forestlike vertically aligned carbon nanotube (VACNT) film, deposited on a silicon (001) substrate by chemical vapor deposition. Tribological experiments were performed using a gold tip under relative humidity varying from 0 to 100%. Very low adhesion forces and high friction coefficients of 0.6–1.3 resulted. The adhesion and friction forces were independent of humidity, due probably to the high hydrophobicity of VACNT. These tribological characteristics were compared to those of a diamond like carbon (DLC) sample.     

Preparation and tribology of aerogel silica and alumina-silica as lubricant oil additives

Aerogel silica and an aerogel mixture of aluminium and silica were prepared using the ethanol supercritical fluid drying technique. Their physical properties were characterised using XRD, transmission electron microscopy, (TEM), and N₂ adsorption. The tribological properties of a 500 SN oil containing the aerogel and a dispersing agent were evaluated using a four-ball machine and a block-on-ring tribotester. Results indicated a greater wear resistance and load-carrying capacity and a lower friction coefficient than for the basic oil. In the oil, the aerogel worked by its deposition on the rubbing surface. Copper stearate was superior to dodecyl alcohol as a dispersing additive, and ultrasonic treatment helped promote the dispersion of the aerogel in oil. There existed an optimum ratio of aluminium isopropyl alcoholate to tetraethanol silicate. The corresponding aerogel mixture gave a maximum value of P_E.     

Tribological Performance of Diamond and Diamondlike Carbon Films at Elevated Temperatures

In this study, the authors investigated the tribological performance of diamond and diamondlike carbon (DLC) films as a function of temperature. Both films were deposited on silicon carbide (SiC) by microwave plasma chemical vapor deposition and ion-beam deposition processes. Tribological tests were performed on a reciprocating wear machine in open air (20 to 30% relative humidity) and under a 10 N load using SiC pins. For the test conditions explored, the steady-state friction coefficients of test pairs without a diamond or DLC film were 0.7 to 0.9 and the average wear rates of pins were 10^?5 to 10^?7 mm³/N·m, depending on ambient temperature. DLC films reduced the steady-slate friction coefficients of the test pairs by factors of three to five and the wear rates of pins by two to three orders of magnitude. Low friction coefficients were also obtained with the diamond films, but wear rates of the counterface pins were high due to the very abrasive nature of these films. The wear of SiC disks coated with either diamond or DLC films was virtually unmeasurable while the wear of uncoated disks was substantial. Test results showed that the DLC films could afford low friction up to about 300° C. At higher temperatures, the DLC films graphitized and were removed from the surface. The diamond films could withstand much higher tempera-lures, but their tribological behavior degraded. Raman spectroscopy and scanning electron microscopy were used to elucidate the friction and wear mechanisms of both films at high temperatures.     

Subsurface damage during dry sliding wear of Al-Al3Ni eutectic alloy

Cylindrical Al-Al₃Ni eutectic alloy wear pins (10 mm in diameter) were slid against a polished steel surface in a pin-on-disc rotating machine under unlubricated conditions with bearing pressures of 6–60 kPa and a constant sliding speed of 70 m min^?1. Metallographic changes in the subsurface region of contact were examined by optical microscopy and microhardness measurements. In the bearing pressure range investigated the alloy exhibited “mild” wear in two linear regions identified as pure “oxidative” wear at low bearing pressures and oxidative with superimposed “metallic” wear at higher bearing pressures. Plastic deformation and fragmentation of the Al₃Ni phase occurred under all bearing pressures. However, in composites prepared by unidirectional solidification containing large Al₃Ni particles fragmentation was insignificant. In all other specimens the size of the fragmented particles in the subsurface region of contact was about 5 μm irrespective of the bearing pressure.     

Tribological behavior between micro- and nano-crystalline diamond films under dry sliding and water lubrication

The tribological behavior of micro- and nano-crystalline diamond films is evaluated in dry sliding and water lubricating condition. The main wear mechanism is found to be abrasive wear mode induced by self-polishing. Non-diamond components and higher compressive residual stresses are detected in flat MCD films after dry sliding, in comparison to NCD. Origin of decreased friction coefficient in CVD diamond tribosystems under water lubrication is attributed to the effect of water on the formed graphic material and the chemisorbing of diamond surface with H₂O, hydrogen or hydroxyl ions. For the MCD/NCD or NCD/MCD contact, the surface roughness of ball largely determines the stable friction coefficient in dry sliding, where NCD film usually presents higher wear rate.     

Ultrananocrystalline Diamond Film as a Wear-Resistant and Protective Coating for Mechanical Seal Applications

Mechanical shaft seals used in pumps are critically important to the safe operation of the paper, pulp, and chemical process industry, as well as petroleum and nuclear power plants. Specifically, these seals prevent the leakage of toxic gases and hazardous chemicals to the environment and final products from the rotating equipment used in manufacturing processes. Diamond coatings have the potential to provide negligible wear, ultralow friction, and high corrosion resistance for the sliding surfaces of mechanical seals, because diamond exhibits outstanding tribological, physical, and chemical properties. However, diamond coatings produced by conventional chemical vapor deposition (CVD) exhibit high surface roughness (R_a ≥ 1 μm), which results in high wear of the seal counterface, leading to premature seal failure. To avoid this problem, we have developed an ultrananocrystalline diamond (UNCD) film formed by a unique CH₄/Ar microwave plasma CVD method. This method yields extremely smooth diamond coatings with surface roughness R_a = 20–30 nm and an average grain size of 2–5 nm. We report the results of a systematic test program involving uncoated and UNCD-coated SiC shaft seals. Results confirmed that the UNCD-coated seals exhibited neither measurable wear nor any leakage during long-duration tests that took 21 days to complete. In addition, the UNCD coatings reduced the frictional torque for seal rotation by five to six times compared with the uncoated seals. This work promises to lead to rotating shaft seals with much improved service life, reduced maintenance cost, reduced leakage of environmentally hazardous materials, and increased energy savings. This technology may also have many other tribological applications involving rolling or sliding contacts.     

Effect of filler composition and crosslinker concentration on the tribological behavior of spent germ particle-based polymeric composites

Thermosetting composites have been prepared by the use of a biobased resin and spent germ filler, which is a byproduct from a wet ethanol production plant. Microscale tribological measurements were performed on samples with different concentrations of the filler as well as the crosslinker using a ball-on-flat reciprocating microtribometer. Microscale friction and wear behavior during dry sliding were evaluated using a spherical silicon nitride probe (radius 1.2 mm) and a conical diamond (radius 100 μm, cone angle 90°) probe to impose different contact conditions. Finally, a pin-on-disc tribometer was used to study the macroscale wear properties at high loads against an alumina pin. Scanning electron microscopy (SEM) images of wear tracks on the samples were obtained to elucidate deformation mechanisms. All samples showed evidence of abrasive wear in both micro- and macro-scales. It was found that an increase in the concentration of the filler resulted in higher friction coefficients against Si₃N₄, while an increase in the concentration of the crosslinker lowered the abrasive wear depth. These results provide some insight into the effectiveness of using biobased spent germ–tung oil polymer composites as potential tribomaterials.     

Influence of surface texture on boundary lubricated sliding contacts

The friction and wear behaviour of boundary lubricated sliding surfaces is influenced by the surface texture. By introducing controlled depressions and undulations in an otherwise flat surface, the tribological properties can be improved. Lubricant can then be supplied even inside the contact by the small reservoirs, resulting in a reduced friction and a prolonged lifetime of the tribological contact.In the present paper, well-defined surface textures were produced by lithography and anisotropic etching of silicon wafers. The wafers were subsequently PVD coated with thin wear resistant TiN or DLC coatings, retaining the substrate texture. The size and shape of the depressions were varied and evaluated in reciprocating sliding under dry and boundary lubricated conditions.     

Transmission Electron Microscopy Analysis of Mo–W–S–Se Film Sliding Contact Obtained by Using Focused Ion Beam Microscope and In Situ Microtribometer

To better understand the fundamentals of solid lubrication, microstructural analyses on the wear scar surface and contact interface of Mo–W–S–Se composite films produced by pulsed laser deposition were completed. Focused ion beam (FIB), transmission electron microscopy (TEM), and X-ray energy dispersive spectroscopy were employed to study the cross-sectional microstructure and chemistry of wear scars. In particular, a novel microtribometer was built for in situ tribological measurements within a FIB microscope. The sliding tip was welded in contact to the wear scar surface on the film under load by re-deposition of sputtering materials from the FIB cut of the tip. Using this technique, cross-sectional TEM specimens were prepared precisely at the contact point without tip/film separation. Here, the in situ FIB microtribometer is critically important for retaining the microstructure of lubricant films as formed at the sliding contact interface between the tip and film without separation. It provides the unique ability to stop sliding, section the contact, and reveal microstructural changes to that contact without disrupting the sliding interface. The cross-sectional TEM measurements were performed on the sliding contact interface for both the regions in contact and just past contact, and both the reorientation and recrystallization of lubricant films were revealed.