Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation.

We have studied the structure of two ionic liquids confined between negatively charged mica sheets. Both liquids exhibit interfacial layering, however the repeat distance is dramatically different for the two liquids. Our results suggest a transition from alternating cation-anion monolayers to tail-to-tail cation bilayers when the length of the cation hydrocarbon chain is increased.

Ionic liquids - salts in the liquid state under ambient conditions - are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition.

Ionic liquids can be intricately nanostructured in the bulk and at interfaces resulting from a delicate interplay between interionic and surface forces. Here we report the structuring of a series of dialkylpyrrolidinium-based ionic liquids induced by confinement. The ionic liquids containing cations with shorter alkyl chain substituents form alternating cation-anion monolayer structures on confinement to a thin film, whereas a cation with a longer alkyl chain substituent leads to bilayer formation. The crossover from monolayer to bilayer structure occurs between chain lengths of n = 8 and 10 for these pyrrolidinium-based ionic liquids. The bilayer structure for n = 10 involves full interdigitation of the alkyl chains; this is in contrast with previous observations for imidazolium-based ionic liquids. The results are pertinent to these liquids' application as electrolytes, where the electrolyte is confined inside the pores of a nanoporous electrode, for example, in devices such as supercapacitors or batteries.

Rate and state friction (RSF) laws are widely used empirical relationships that describe the macroscale frictional behavior of a broad range of materials, including rocks found in the seismogenic zone of Earth's crust. A fundamental aspect of the RSF laws is frictional "aging," where friction increases with the time of stationary contact due to asperity creep and/or interfacial strengthening. Recent atomic force microscope (AFM) experiments and simulations found that nanoscale silica contacts exhibit aging due to the progressive formation of interfacial chemical bonds. The role of normal load (and, thus, normal stress) on this interfacial chemical bond-induced (ICBI) friction is predicted to be significant but has not been examined experimentally. Here, we show using AFM that, for nanoscale ICBI friction of silica-silica interfaces, aging (the difference between the maximum static friction and the kinetic friction) increases approximately linearly with the product of the normal load and the log of the hold time. This behavior is attributed to the approximately linear dependence of the contact area on the load in the positive load regime before significant wear occurs, as inferred from sliding friction measurements. This implies that the average pressure, and thus the average bond formation rate, is load independent within the accessible load range. We also consider a more accurate nonlinear model for the contact area, from which we extract the activation volume and the average stress-free energy barrier to the aging process. Our work provides an approach for studying the load and time dependence of contact aging at the nanoscale and further establishes RSF laws for nanoscale asperity contacts.

Atomically flat and clean metal surfaces exhibit a regime of ultra-low friction at low normal loads. Atomic force microscopy, performed in ultra-high vacuum on Cu(100) and Au(111) surfaces, reveals a clear stick-slip modulation in the lateral force but almost zero dissipation. Significant friction is observed only for higher loads (*4-6 nN above the pull-off force) together with the onset of wear. We discuss the minor role of thermal activation in the low friction regime and suggest that a compliant metallic neck between tip and surface is formed which brings upon the low, load-independent shear stress.

Using frequency-modulation atomic force microscopy ͑FM-AFM͒ at sub-nanometer vibration amplitudes, we find in the system n-dodecanol/graphite that solvation layers may extend for several nanometers into the bulk liquid. These layers maintain crystalline order which can be imaged using FM-AFM. The energy dissipation of the vibrating tip can peak sharply upon penetration of molecular layers. The tip shape appears critical for this effect.A notable property of liquid near the liquid-solid interface is the presence of solvation layers, i.e., ordering of liquid molecules due to boundary conditions imposed by the solid. Such layering has been observed via oscillatory solvation forces when confining the liquid between the substrate and a solid probe using the surface force apparatus 1 and atomic force microscopy ͑AFM͒. 2,3 While solvation forces are routinely detected via the modulation of the force, the lateral structure of the solvation shells-beyond the first adsorbed monolayer-has rarely been directly observed. One exception are long-chain alkanes adsorbed from solution, for which a second layer has been imaged using scanning tunneling microscopy ͑STM͒. 4 Unfortunately, STM does not lend itself to imaging of "higher" layers as the tunneling current decreases exponentially with the thickness of the confined ͑nonconductive͒ liquid. The lamellar structure of a second solvation layer of hexadecane was imaged recently using a tuning fork AFM. 5 There remain open questions about the structure of higher solvation layers, namely, whether they exhibit lateral order. These questions will become increasingly important for high-resolution AFM imaging in liquid, in particular, for hydration layers in biological systems. 6,7 The development of instrumentation capable of smallamplitude, frequency-modulated AFM ͑FM-AFM͒ ͑Ref. 8͒ in liquid environments 9 has dramatically increased the resolution and sensitivity achievable in AFM studies in liquid. We apply FM-AFM to a linear alcohol ͑dodecanol͒ on an atomically flat graphite substrate slightly above the bulk freezing temperature. We find not only spectroscopic evidence of multiple solvation layers, i.e., force oscillations but also obtain real-space topography images of the alcohol molecules in higher layers, demonstrating that the solvation layers in this system have a crystalline structure. Further we sometimes observe, depending on the condition of the tip, sharp peaks in the mechanical dissipation just as a solvation layer is squeezed out of the tip-sample gap.To achieve the sensitivity necessary for molecular resolution AFM in liquid, a commercial AFM ͑Molecular Imaging Picoscope͒ was modified. Changes to the optical beam deflection sensor include replacement of the standard laser source with a home-built, rf-modulated diode laser 9 and modification of the focusing optics to achieve a smaller numerical aperture. Using standard silicon cantilevers ͑type NCLR, Nanosensors, Neuchatel, Switzerland and type ACLA, AppNano, Santa Clara, CA͒ with a spring constant of k c Ϸ 40 N / m, a ...

We present a magnetic force-based direct drive modulation method to measure local nano-rheological properties of soft materials across a broad frequency range (10 Hz to 2 kHz) using colloid-attached atomic force microscope (AFM) probes in liquid. The direct drive method enables artefact-free measurements over several decades of excitation frequency, and avoids the need to evaluate medium-induced hydrodynamic drag effects. The method was applied to measure the local mechanical properties of polyacrylamide hydrogels. The frequency-dependent storage stiffness, loss stiffness, and loss tangent (tan δ) were quantified for hydrogels having high and low crosslinking densities by measuring the amplitude and the phase response of the cantilever while the colloid was in contact with the hydrogel. The frequency bandwidth was further expanded to lower effective frequencies (0.1 Hz to 10 Hz) by obtaining force–displacement (FD) curves. Slow FD measurements showed a recoverable but highly hysteretic response, with the contact mechanical behaviour dependent on the loading direction: approach curves showed Hertzian behaviour while retraction curves fit the JKR contact mechanics model well into the adhesive regime, after which multiple detachment instabilities occurred. Using small amplitude dynamic modulation to explore faster rates, the load dependence of the storage stiffness transitioned from Hertzian to a dynamic punch-type (constant contact area) model, indicating significant influence of material dissipation coupled with adhesion. Using the appropriate contact model across the full frequency range measured, the storage moduli were found to remain nearly constant until an increase began near ∼100 Hz. The softer gels' storage modulus increased from 7.9 ± 0.4 to 14.5 ± 2.1 kPa (∼85%), and the stiffer gels' storage modulus increased from 16.3 ± 1.1 to 31.7 ± 5.0 kPa (∼95%). This increase at high frequencies may be attributed to a contribution from solvent confinement in the hydrogel (poroelasticity). The storage moduli measured by both macro-rheometry and AFM FD curves were comparable to those measured using the modulation method at their overlapping frequencies (10–25 Hz). In all cases, care was taken to ensure the contact mechanics models were applied within the important limit of small relative deformations. This study thus highlights possible transitions in the probe–material contact mechanical behaviour for soft matter, especially when the applied strain rates and the material relaxation rates become comparable. In particular, at low frequencies, the modulus follows Hertzian contact mechanics, while at high frequencies adhesive contact is well represented by punch-like behaviour. More generally, use of the Hertz model on hydrogels at high loading rates, at high strains, or during the retraction portion of FD curves, leads to significant errors in the calculated moduli.