Microfriction and macrofriction of metal containing amorphous hydrocarbon hard coatings determined by AFM and pin‐on‐disk tests

Metal containing amorphous hydrocarbon films (Me‐C:H) have excellent tribological properties and an adjustable electrical conductivity. Friction force microscopy investigations on gold‐ and tungsten‐C:H films show a non‐linear dependence of friction on the load in the nanonewton‐range which can be explained by Hertz model of elastic contact. The effective friction coefficient and the interfacial shear stress strongly depend on the type of metal and the metal concentration inside the film. Microfriction and macrofriction (pin‐on‐disk) show a high qualitative correspondence. This revised version was published online in June 2006 with corrections to the Cover Date.     

Simulations of friction anisotropy on ordered organic monolayer

A method of molecular dynamics is used to investigate friction anisotropy observed on a hexagonally packed organic monolayer of straight-chain molecules, which tilt in a specific direction. A rigid gold slider with a single atomic protuberance is used as a model of a typical atomic force microscope tip apex. The friction anisotropy is observed at 50 K, which is below the melting point of rotation around a long axis of the molecule. The anisotropic frictional behavior is that sliding in directions normal to the direction of the collective tilt of the molecules results in the maximum friction force. The origin of the anisotropy is attributed to anisotropy in lateral compliance in the monolayer.     

Friction force microscopy investigations of potassium halide surfaces in ultrahigh vacuum: structure,friction and surface modification

Friction force microscopy measurements on the vacuum‐cleaved (001) surfaces of KF, KCl and KBr have been carried out. All surfaces exhibit atomically flat terraces with monatomic steps aligned preferentially along low‐index lattice directions. Stick‐slip lateral forces with the lattice periodicity are observed on all surfaces. Tip‐sample contact creates higher friction domains on the terraces of all three materials. The structure, topography and degree of friction force contrast of these domains is material dependent. The dependence of friction upon load generally does not coincide with the behavior expected for an elastic contact. We propose that the observed domains result from surface structural changes created by low load tip‐sample contact on these relatively soft materials. This revised version was published online in June 2006 with corrections to the Cover Date.     

Stick–slip motion in the atomic force microscope

Measurements of atomic friction in the atomic force microscope frequently show periodic variations at the lattice spacing of the surface being scanned, which have the saw‐tooth wave form characteristic of “stick–slip” motion. Simple models of this behaviour have been proposed, in which the “dynamic element” of the system is provided by the elastic stiffness and inertia of the cantilever which supports the tip of the microscope, in its lateral, i.e., torsional mode of vibration. These models have been successful in predicting the observed motion, but only by assuming that the cantilever is heavily damped. However, the source of this damping in a highly elastic cantilever is not explained. To resolve the paradox, it is shown in this note that it is necessary to introduce the elastic stiffness of the contact into the model. The relationship between the contact stiffness, the cantilever stiffness and the amplitude of the periodic friction force is derived in order for stick–slip motion at lattice spacing to be achieved. This revised version was published online in July 2006 with corrections to the Cover Date.     

Observation of proportionality between friction and contact area at the nanometer scale

The nanotribological properties of a hydrogen‐terminated diamond(111)/tungsten‐carbide interface have been studied using ultra‐high vacuum atomic force microscopy. Both friction and local contact conductance were measured as a function of applied load. The contact conductance experiments provide a direct and independent way of determining the contact area between the conductive tungsten‐carbide AFM tip and the doped diamond sample. We demonstrate that the friction force is directly proportional to the real area of contact at the nanometer‐scale. Furthermore, the relation between the contact area and load for this extremely hard heterocontact is found to be in excellent agreement with the Derjaguin–Müller–Toporov continuum mechanics model. This revised version was published online in September 2006 with corrections to the Cover Date.     

Macro- and nanotribological properties of organosilane monolayers prepared by a chemical vapor adsorption method on silicon substrates

Organosilane monolayers are novel ultrathin films used to control the physicochemical properties, such as friction and wear, of solid surfaces. In this study, the authors prepared alkylsilane and fluoroalkylsilane monolayers with a series of chain lengths by a chemical vapor adsorption method. The monolayers tribological properties were investigated by lateral force microscope (LFM) and friction tester. LFM nanoscale measurements of tribological properties showed that alkylsilane monolayer gave lower lateral force than the Si substrate surface. The lateral force decreased as the length of the alkyl chain increased. On the macroscale, friction test revealed that the organosilane monolayers gave lower dynamic friction coefficients than the Si substrate surface in air at room temperature. The longer the alkyl chain, the greater the wear resistance of the organosilane monolayers. Friction experiments using tetradecane as a lubricant showed better tribological properties than were obtained in air. Furthermore, microscopically line-patterned two-component organosilane monolayers were prepared and their macroscopic friction behavior was investigated. Even though the height difference between the two-components was less than 1 nm, friction force anisotropy between the parallel and perpendicular directions against the line pattern was observed.     

Shear-induced mechanochromism in polydiacetylene monolayers

We use atomic force microscopy to actuate and characterize the nanoscale mechanochromism of polydiacetylene monolayers on atomically-flat silicon oxide substrates. We find explicit evidence that the irreversible blue-to-red transformation is caused by shear forces exerted normal to the polydiacetylene polymer backbone. The anisotropic probe-induced transformation is characterized by a significant change in the tilt orientation of the side chains with respect to the surface normal. We discuss preliminary molecular dynamics simulations and electronic structure calculations on twelve-unit polydiacetylene oligomers that allow us to correlate the transformation with bond-angle changes in the conjugated polymer backbone.     

A new calibration method of the lateral contact stiffness and lateral force using modulated lateral force microscopy

We describe a new calibration method for lateral contact stiffness using modulated lateral force microscopy, a technique that offers some advantages with respect to the more classical friction force microscopy currently used for characterizing the friction properties of materials. The calibration method is based on the study of the lateral contact stiffness versus applied load and on the use of elasticity contact theories to determine by fit the calibration coefficient, allowing the scaling of experimental data. The method is tested by measuring the friction coefficient and shear strength of silicon and mica samples, respectively, and compared with results from the literature. This revised version was published online in August 2006 with corrections to the Cover Date.     

Tribological behaviour of modified polyacetal against MC nylon without lubrication

Compared with other polymers, polyacetal or polyoxymethylene (POM) which is widely used as bearing, guide, gear and other sliding parts, has high strength and stiffness, excellent chemical resistance and superior antifriction and wear resistance. To improve the toughness and self‐lubrication capacity of POM due to its higher crystallizability, other components, which include toughening phase and solid lubricants, are often added to the POM matrix. This paper deals with the friction and wear behaviours of POM which was modified by the toughening phase polyurethane (PU) and filled with polytetrafluoroethylene (PTFE) and silicone oil, during rubbing against MC nylon without liquid lubrication. Friction and wear tests show the tribological performance of the modified POM (M‐POM) with 10 wt% PU is better than those of pure POM and POM blended with PTFE under dry friction. The frictional coefficient of the M‐POM decreases with increasing nominal load. The sliding velocity has a more obvious effect on the tribological properties of the M‐POM than the nominal load. The higher sliding velocity leads to thermal degradation and melting of the experimental polymers because of the frictional heat. This revised version was published online in June 2006 with corrections to the Cover Date.     

Friction,Wear, and Aging of an Alkoxy-monolayer Boundary Lubricant on Silicon

We study the friction, wear, and aging of a model boundary lubricant, an alkoxy monolayer covalently bonded to a Si(111) surface, using an interfacial force microscope with a spherical diamond probe. The robust alkoxy bond creates a film that effectively lubricates and prevents wear of Si at stresses comparable to those found in microelectromechanical systems devices. Sliding on the monolayer over 50 nm produced friction approximately three times greater than that of sliding over molecular length scales (∼2 nm); this is attributed to deformation dynamics of the experiment. By repeated scanning over the same location, we observed wear on a level that reduces the friction by thinning and/or reordering the monolayer film.     

Surface chemistry-mechanical property relationship of low density polyethylene: an IR+visible sum frequency generation spectroscopy and atomic force microscopy study

Surface-specific IR+visible sum frequency generation (SFG) spectroscopy was used to obtain chemical composition of two polymer surfaces. The SFG surface vibrational spectrum of pure low density polyethylene and that of a commercial sample of the same kind of polymer, which contains additives, are markedly different. This correlates well with the very different surface mechanical properties, i.e., stiffness (indicative of the elastic modulus) and friction, which were measured by atomic force microscopy (AFM) on the same polymer surfaces. The surface of CLDPE is dominated by methoxy (−OCH₃) contained additives, segregated from the bulk, which explains a lower stiffness, adhesion and friction of the surface, as measured by AFM. This revised version was published online in August 2006 with corrections to the Cover Date.     

Velocity dependent friction laws in contact mode atomic force microscopy

Friction forces in the tip–sample contact govern the dynamics of contact mode atomic force microscopy. In ambient conditions typical contact radii between tip and sample are in the order of a few nanometers. In order to account for the large interaction area the dynamics of contact mode atomic force microscope (AFM) is investigated under the assumption of a multi-asperity contact interface between tip and sample. Thus, the kinetic friction force between tip and sample is the product of the real contact area between both solids and the interfacial shear strength. The velocity strengthening of the lateral force is modeled assuming a logarithmic relationship between shear-strength and velocity. Numerical simulations of the system dynamics with this empirical model show the existence of two different regimes in contact mode AFM: steady sliding and stick–slip where the tip undergoes periodically stiction and kinetic friction. The state of the system depends on the scan velocity as well as on the velocity dependence of the interfacial friction force between tip and sample. Already small viscous damping contributions in the tip–sample contact are sufficient to suppress stick–slip oscillations.     

Exploring the “friction modifier” phenomenon: nanorheology of n‐alkane chains with polar terminus dissolved in n‐alkane solvent

Dilute solutions of two polar end‐functionalized linear alkanes (1‐hexadecylamine and palmitic acid), each dissolved in tetradecane, were confined between two mica surfaces and investigated using a surface forces apparatus modified to study shear nanorheology. These two solutions showed similar nanorheological properties that differed from those observed for pure n‐alkanes. In static measurements, a “hard wall”, rather than an oscillatory force, was observed as a function of film thickness. The polar alkane component formed a weakly adsorbed single layer at each mica surface, disrupting the layered structures found in neat n‐tetradecane. In dynamic experiments at low shear amplitude, the storage modulus G' exceeded the loss modulus G" at low frequencies; above some characteristic frequencies G' increased such that g' ≈ G", indicating significantly more energy loss through viscous modes at higher frequency. When the amplitude was varied at fixed frequency, no stick–slip was observed and the limiting value of the shear stress at high effective shear rate was an order of magnitude less than for unfunctionalized n‐alkanes at similar loads. Together, these results show that the addition of a small amount of polar alkane component, by disrupting the layered structures that would have been formed in the neat n‐alkane, is effective in suppressing static friction and reducing kinetic friction in the boundary lubrication regime. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tribological Properties of Alkoxyl Monolayers on Oxide Terminated Silicon

The tribological properties of alkoxyl monolayers on oxide terminated silicon surfaces have been investigated using interfacial force microscopy. For a C18 alkoxyl monolayer, both adhesion and frictional properties are similar to those of a self-assembled monolayer of octadecanethiol on gold. Friction is shown to increase as the alkyl chain length of the molecules decreases. Analysis using contact mechanics models has been carried out to estimate reduced modulus, adhesion energy, and friction shear strength. These interfacial mechanical properties are correlated to molecular structures at the interface.     

Adhesion and wear of colloidal silica probed by force microscopy

The adhesion and wear of colloidal silica nanoparticles (50 nm diameter) dispersed in a film have been directly studied using atomic force microscopy (AFM) under aqueous solution conditions. The adhesion between surface‐bound silica particles and the AFM tip is found to peak in strength between pH 4 and 5. Using the JKR contact mechanics model, the energy for a single Si–OH/Si–OH interaction was estimated to be 0.4 ± 0.1 kcal/mol. Tribochemical wear of the silica particles, and their displacement from the film, is enhanced at high pH due to the increased facility of silica dissolution and the concomitant increase in attendant inter‐particle repulsion. This revised version was published online in September 2006 with corrections to the Cover Date.     

Dynamic friction measurements with an atomic force microscope on polymer surfaces

The combination of scanning friction force microscopy (SFFM) and lock‐in techniques leads to dynamic SFFM (DSFFM) and provides great advantages in friction force studies with sub‐micrometre resolution. In this paper are presented measurements on thin adsorbed organic films on polymers (polymer blend of 75% poly(allylaminehydrochloride) (PAA) and 25% poly(diallyl‐dimethylammonium chloride) (PDDAC)) and on mica (as a reference). The amplitude and phase response as a function of the excitation amplitude can be explained on hard surfaces by a simple static and dynamic friction model. This model allows us further to distinguish static friction forces and kinetic friction forces in a quantitative way. Furthermore, we demonstrate the use of these spectra to determine the correct modulation amplitude of the excitation to achieve the optimal friction contrasts directly. Polymer data suggest that the viscoelastic shear flow under the atomic force microscope (AFM) tip is responsible for the shape of the phase and amplitude spectrum. Lastly, we demonstrate that DSFFM is a useful technique for surface characterisation in situations where SFFM may not be adequate.     

Evaluations of tribological characteristics of PFPE lubricants on DLC surfaces of magnetic disks

This article presents measurements of adhesion and friction of perfluoropolyether (PFPE) lubricant films dip-coated on magnetic disks covered with diamond-like carbon (DLC) film. We have developed a custom-built pin-on-disk type micro-tribotester to perform the tribological measurements. The adhesion tests were performed by pulling down/up a 1.5-mm-diameter glass ball on a stationary disk surface, and the friction tests were carried out by sliding the glass ball on a rotating disk surface without changing head-disk interface conditions from the adhesion tests. Experiments were performed for the different kinds of 2- and 6-nm-thick PFPE lubricants (polar: Zdol4000 and Zdol2000; nonpolar: Z03) under lightly loaded and slow sliding conditions to minimize disturbance against the molecular layered structure. The adhesive forces were found to decrease with increasing film thickness in the order of Z03 > Zdol2000 > Zdol4000 (decreasing rate), which closely corresponds to the order of monolayer thickness, and then to saturate to almost the same calculated values. As for the friction forces of 2-nm-thick films, Zdol2000 featured extraordinarily large friction in comparison with Zdol4000 and Z03, while Zdol4000 was slightly larger than Z03. The largest friction of Zdol2000 reveals that the 2-nm-thick Zdol2000 formed a monolayer that served as an immobile layer. With the increase in film thickness, the friction force of Zdol2000 decreased, indicating that extra lubricant molecules served as a mobile layer, while that of Z03 remained unchanged as the lowest value. By extrapolating the loading force versus friction force relationship into a negative loading force region, it is found that the friction force of Z03 tended to zero at zero net load (loading force plus adhesion force), while those for Zdol2000 and Zdol4000 exhibited finite values, indicating formation of an immobile layer, which shows similar characteristics to those of adhesive rubber material. The dewetted surface is found to feature violently changing friction force only at the first stage of sliding, and it then becomes stable after several sliding passes.     

Investigation of human hair fibers using lateral force microscopy

Atomic force microscopy (AFM) and lateral force microscopy (LFM) were used to investigate the morphologic and surface changes associated with various surface modifications to human hair. These included extraction with a series of solvents, bleaching, and treatment with a cationic copolymer. The study assessed the ability of these techniques to distinguish the changes in surface properties, including morphology and friction coefficient, as manifested in changes brought about by the indicated surface modifications. While topographic morphology can easily be investigated with contact AFM. LFM offers an additional tool for probing the surface distribution of oils and waxes. The removal of surface lipids from the fiber surface was accomplished using soxhlet extraction with t-butanol and n-hexane, while the free internal lipids (within the fiber structure) were removed by extraction with a mixture of chloroform and methanol (70:30, v/v). In addition, the surface of hair was modified with the cationic polymer, co(vinyl pyrrolidone-methacrylamidopropyl trimethylammonium chloride [PVP/MAPTAC]), and its distribution on the surface was monitored. Ambient AFM and LFM studies of surface modified and native fibers clearly indicate that when investigated as a function of tip loading force, the different modifications result in changes of the friction coefficient, which increase in this order: native, bleached, solvent extracted, and polymer-treated hair. Friction images show surface variations that are interpreted as areas of varying lipid film coverage. In addition, topographic images of the fibers show the presence of small pores, which become increasingly prevalent upon solvent extraction.     

A novel AFM based method for force measurements between individual hair strands

Interactions between hairs and other natural fibers are of broad interest for both applications and fundamental understanding of biological interfaces. We present a novel method, that allows force measurements between individual hair strands. Hair fragments can be laser-cut without altering their surface chemistry. Subsequently, they are glued onto Atomic force microscopy (AFM) cantilevers. This allows carrying out measurements between the hair fragment and surface immobilized hair in a well-defined crossed-cylinder geometry. Both force–distance and friction measurements are feasible. Measurements in air with controlled humidity and in aqueous environment show clear differences which can be explained by the dominating role of capillary interactions in air. Friction is found to be anisotropic, reflecting the fine structure of hair cuticula. While the investigations are focused on the particular example of human hair, we expect that the approach can be extended to other animal/plant fibers and thus offers perspectives for broad spectrum systems.     

Boundary lubrication additives for aluminium: A journey from nano to macrotribology

The tribology of two potential additive molecules for aluminium has been studied in the self assembled monolayer state at low loads (10⁻⁹–10⁻² N) and in dispersion state in n-hexadecane at high load (60 N). The two additive molecules are 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (FOTS), which has a rigid rod-like helical structure and octadecyltrichlorosilane (OTS), which has a zigzag backbone configuration. The adhesion, friction and wear performance have been investigated. Molecular conformational order and stiffness were found to play major roles in frictional dissipation and wear resistance, recorded in a nanotribometer and a pin-on-disc machine, while for very low load measurements (LFM), adhesion was found to have a significant role on friction along with molecular entropy.