Resolving Multi-Asperity Contacts at the Nanoscale through Super-Resolution Fluorescence Imaging.

Contact mechanics, spanning nanometer to tectonic scales, faces long-standing challenges arising from multiscale random roughness, which hinders experimental validation of theories. Understanding multi-asperity rough contacts is vital for addressing catastrophic consequences of these contacts failing such as earthquakes and for diverse technological applications. To visualize such contacts, we introduce a super-resolution microscopy method utilizing spontaneous millisecond ON/OFF fluorescence blinking of contact-sensitive molecular rotor molecules immobilized on a glass coverslip. This technique achieves ∼55 nm lateral imaging resolution for rough poly(methyl methacrylate) and glass spheres on glass contacts. For soft polymer spheres due to large plastic deformation, the resolution improvement does not significantly affect the area of real contact. However, for hard glass spheres, the real contact area is found to be 2.4 times smaller than that found by diffraction-limited imaging. This study highlights, through direct visualization, the impact of material stiffness on the nanoscale structure within the area of real contact.

Controlling Macroscopic Friction through Interfacial Siloxane Bonding.

Controlling macroscopic friction is crucial for numerous natural and industrial applications, ranging from forecasting earthquakes to miniaturizing semiconductor devices, but predicting and manipulating friction phenomena remains a challenge due to the unknown relationship between nanoscale and macroscopic friction. Here, we show experimentally that dry friction at multiasperity Si-on-Si interfaces is dominated by the formation of interfacial siloxane (Si─O─Si) bonds, the density of which can be precisely regulated by exposing plasma-cleaned silicon surfaces to dry nitrogen. Our results show how the bond density can be used to quantitatively understand and control the macroscopic friction. Our findings establish a unique connection between the molecular scale at which adhesion occurs, and the friction coefficient that is the key macroscopic parameter for industrial and natural tribology challenges.

The nucleation, growth, and adhesion of water bridges in sliding nano-contacts.

We provide experimental observations of the nucleation and growth of water capillary bridges in nanometer gaps between a laterally moving atomic force microscope probe and a smooth silicon wafer. We find rising nucleation rates with increasing lateral velocity and a smaller separation gap. The interplay between nucleation rate and lateral velocity is attributed to the entrainment of water molecules into the gap by the combination of lateral motion and collisions of the water molecules with the surfaces of the interface. The capillary volume of the full-grown water bridge increases with the distance between the two surfaces and can be limited by lateral shearing at high velocities. Our experimental results demonstrate a novel method to study in situ how water diffusion and transport impact dynamic interfaces at the nanoscale, ultimately leading to friction and adhesion forces at the macroscale.

Why Teflon is so slippery while other polymers are not.

Polytetrafluoroethylene [PTFE (Teflon)] is a uniquely slippery polymer, with a coefficient of friction that is an order of magnitude lower than that of other polymers. Though known as nonsticky, PTFE leaves a layer of material behind on the substrate while sliding. Here, we use contact-sensitive fluorescent probes to image the sliding contact in situ: We show that slip happens at an internal PTFE-PTFE interface that has an unusually low shear strength of 0.8 MPa. This weak internal interface directly leads to low friction and enables transfer of the PTFE film to the substrate even in the absence of strong adhesion.

Molecular Probing of the Stress Activation Volume in Vapor Phase Lubricated Friction.

When two solid objects slide over each other, friction results from the interactions between the asperities of the (invariably rough) surfaces. Lubrication happens when viscous lubricants separate the two surfaces and carry the load such that solid-on-solid contacts are avoided. Yet, even small amounts of low-viscosity lubricants can still significantly lower friction through a process called boundary lubrication. Understanding the origin of the boundary lubricating effect is hampered by challenges in measuring the interfacial properties of lubricants directly between the two surfaces. Here, we use rigidochromic fluorescent probe molecules to measure precisely what happens on a molecular scale during vapor-phase boundary lubrication of a polymer bead-on-glass interface. The probe molecules have a longer fluorescence lifetime in a confined environment, which allows one to measure the area of real contact between rough surfaces and infer the shear stress at the lubricated interfaces. The latter is shown to be proportional to the inverse of the local interfacial free volume determined using the measured fluorescence lifetime. The free volume can then be used in an Eyring-type model as the stress activation volume, allowing to collapse the data of stress as a function of sliding velocity and partial pressure of the vapor phase lubricant. This shows directly that as more boundary lubricant is applied, larger clusters of lubricant molecules become involved in the shear process thereby lowering the friction.

Local Shearing Force Measurement during Frictional Sliding Using Fluorogenic Mechanophores.

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

Nonmonotonic Friction due to Water Capillary Adhesion and Hydrogen Bonding at Multiasperity Interfaces.

Capillary adhesion due to water adsorption from the air can contribute to friction, especially for smooth interfaces in humid environments. We show that for multiasperity (naturally oxidized) Si-on-Si interfaces, the friction coefficient goes through a maximum as a function of relative humidity. An adhesion model based on the boundary element method that takes the roughness of the interfaces into account reproduces this nonmonotonic behavior very well. Remarkably, we find the dry friction to be significantly lower than the lubricated friction with macroscopic amounts of water present. The difference is attributed to the hydrogen-bonding network across the interface. Accordingly, the lubricated friction increases significantly if the water is replaced by heavy water (D_{2}O) with stronger hydrogen bonding.

Photophysics of Fluorescent Contact Sensors Based on the Dicyanodihydrofuran Motif.

Fluorescent molecular rotors have been used for measurements of local mobility on molecular length scales, for example to determine viscosity, and for the visualization of contact between two surfaces. In the present work, we deepen our insight into the excited-state deactivation kinetics and mechanics of dicyanodihydrofuran-based molecular rotors. We extend the scope of the use of this class of rotors for contact sensing with a red-shifted member of the family. This allows for contact detection with a range of excitation wavelengths up to ∼600 nm. Steady-state fluorescence shows that the fluorescence quantum yield of these rotors depends not only on the rigidity of their environment, but - under certain conditions - also on its polarity. While excited state decay via rotation about the exocyclic double bond is rapid in nonpolar solvents and twisting of a single bond allows for fast decay in polar solvents, the barriers for both processes are significant in solvents of intermediate polarity. This effect may also occur in other molecular rotors, and it should be considered when applying such molecules as local mobility probes.

Fluorescence microscopy visualization of the roughness-induced transition between lubrication regimes.

We investigate the transition between different regimes of lubrication and directly observe the thickness of nanometric lubrication films with a sensitivity of a single molecular layer at a multi-asperity interface through fluorescence microscopy. We redefine specific film thickness as the ratio of the lubricant film thickness and the surface roughness measured only at those regions of the interface where the gap is "minimal." This novel definition of specific film thickness successfully captures the transition from full elastohydrodynamic lubrication to mixed and boundary lubrication. The transition can be triggered by increasing the surface roughness and is accurately predicted by using the new film thickness definition. We find that when the liquid carries part of the load, its apparent viscosity is greatly increased by confinement, and show how the transition between different lubrication regimes is well described by the viscosity increase and subsequent glass transition in the film.

Fast 3D Microscopy Imaging of Contacts Between Surfaces Using a Fluorescent Liquid.

A novel method is presented for the rapid direct 3D visualization of the contact between two surfaces by means of fluorescence microscopy using a fluorescent liquid. Distances between the surfaces of up to several hundred nanometers can be determined with subnanometer accuracy in 3D and within seconds of measurement time. The method opens new possibilities for research in the areas of contact mechanics, friction, wear, and lubrication.

Molecular Insight into the Slipperiness of Ice.

Measurements of the friction coefficient of steel-on-ice over a large temperature range reveal very high friction at low temperatures (-100 °C) and a steep decrease in the friction coefficient with increasing temperature. Very low friction is only found over the limited temperature range typical for ice skating. The strong decrease in the friction coefficient with increasing temperature exhibits Arrhenius behavior with an activation energy of Ea ≈ 11.5 kJ mol-1. Remarkably, molecular dynamics simulations of the ice-air interface reveal a very similar activation energy for the mobility of surface molecules. Weakly hydrogen-bonded surface molecules diffuse over the surface in a rolling motion, their number and mobility increasing with increasing temperature. This correlation between macroscopic friction and microscopic molecular mobility indicates that slippery ice arises from the high mobility of its surface molecules, making the ice surface smooth and the shearing of the weakly bonded surface molecules easy.

S-shaped flow curves of shear thickening suspensions: direct observation of frictional rheology.

We study the rheological behavior of concentrated granular suspensions of simple spherical particles. Under controlled stress, the system exhibits an S-shaped flow curve (stress vs shear rate) with a negative slope in between the low-viscosity Newtonian regime and the shear thickened regime. Under controlled shear rate, a discontinuous transition between the two states is observed. Stress visualization experiments with a fluorescent probe suggest that friction is at the origin of shear thickening. Stress visualization shows that the stress in the system remains homogeneous (no shear banding) if a stress is imposed that is intermediate between the high- and low-stress branches. The S-shaped shear thickening is then due to the discontinuous formation of a frictional force network between particles upon increasing the stress.

Fluorescence microscopy visualization of contacts between objects.

The area of contact between two objects was detected by using the strong enhancement of the fluorescence of rigidochromic probe molecules attached to one of the surfaces. Confinement of the molecules suppresses nonradiative decay and turns on the fluorescence. The approach is demonstrated by imaging of the contact area of a plastic sphere in contact with a flat glass surface. Our results agree excellently with the prediction of Hertz's classical theory based on elastic deformation.

Colloidal aggregation in microgravity by critical Casimir forces.

By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of near field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as in the kinetics of growth. In microgravity purely diffusive aggregation is observed. By using the continuously variable particle interaction potential we can for the first time experimentally relate the strength of attraction between the particles and the structure of the aggregates.