Thomas Salez

A Direct Quantitative Measure of Surface Mobility in a Glassy Polymer

Polymer Film Behavior An ongoing debate in the understanding of the behavior of thin-film glassy polymers is whether there is nanoconfinement of large molecules or enhanced mobility near a free surface. Chai et al. (p. 994; see the Perspective by Chen et al.) prepared polymer films with a sharp step in the profile by depositing broken film fragments onto a uniform underlay. Atomic force microscopy revealed changes to the overall film profile with time at various temperatures. A transition was observed from localized motions to relaxation of the entire film at a temperature close to that of the bulk glass transition temperature. A step geometry is used to probe the behavior of a glassy polymer above and below its glass transition temperature. [Also see Perspective by Chen et al.] Thin polymer films have striking dynamical properties that differ from their bulk counterparts. With the simple geometry of a stepped polymer film on a substrate, we probe mobility above and below the glass transition temperature Tg. Above Tg the entire film flows, whereas below Tg only the near-surface region responds to the excess interfacial energy. An analytical thin-film model for flow limited to the free surface region shows excellent agreement with sub-Tg data. The system transitions from whole-film flow to surface localized flow over a narrow temperature region near the bulk Tg. The experiments and model provide a measure of surface mobility in a simple geometry where confinement and substrate effects are negligible. This fine control of the glassy rheology is of key interest to nanolithography among numerous other applications.

Indentation of a rigid sphere into an elastic substrate with surface tension and adhesion

The surface tension of compliant materials such as gels provides resistance to deformation in addition to and sometimes surpassing that owing to elasticity. This paper studies how surface tension changes the contact mechanics of a small hard sphere indenting a soft elastic substrate. Previous studies have examined the special case where the external load is zero, so contact is driven by adhesion alone. Here, we tackle the much more complicated problem where, in addition to adhesion, deformation is driven by an indentation force. We present an exact solution based on small strain theory. The relation between indentation force (displacement) and contact radius is found to depend on a single dimensionless parameter: ω=σ(μR)−2/3((9π/4)Wad)−1/3, where σ and μ are the surface tension and shear modulus of the substrate, R is the sphere radius and Wad is the interfacial work of adhesion. Our theory reduces to the Johnson–Kendall–Roberts (JKR) theory and Young–Dupre equation in the limits of small and large ω, respectively, and compares well with existing experimental data. Our results show that, although surface tension can significantly affect the indentation force, the magnitude of the pull-off load in the partial wetting liquid-like limit is reduced only by one-third compared with the JKR limit and the pull-off behaviour is completely determined by ω.

Self-similarity and energy dissipation in stepped polymer films.

The surface of a thin liquid film with a nonconstant curvature is unstable, as the Laplace pressure drives a flow mediated by viscosity. We present the results of experiments on one of the simplest variable curvature surfaces: a thin polymer film with a step. Height profiles are measured as a function of time for a variety of molecular weights. The evolution of the profiles is shown to be self-similar. This self-similarity offers a precise measurement of the capillary velocity by comparison with numerical solutions of the thin film equation. We also derive a master expression for the time dependence of the excess free energy as a function of the material properties and film geometry. The experiment and theory are in excellent agreement and indicate the effectiveness of stepped polymer films to elucidate nanoscale rheological properties.

Influence of slip on the Plateau-Rayleigh instability on a fibre

The Plateau–Rayleigh instability of a liquid column underlies a variety of fascinating phenomena that can be observed in everyday life. In contrast to the case of a free liquid cylinder, describing the evolution of a liquid layer on a solid fibre requires consideration of the solid–liquid interface. Here we revisit the Plateau–Rayleigh instability of a liquid coating a fibre by varying the hydrodynamic boundary condition at the fibre–liquid interface, from no slip to slip. Although the wavelength is not sensitive to the solid–liquid interface, we find that the growth rate of the undulations strongly depends on the hydrodynamic boundary condition. The experiments are in excellent agreement with a new thin-film theory incorporating slip, thus providing an original, quantitative and robust tool to measure slip lengths.

Self-sustained lift and low friction via soft lubrication

Significance Contacting solids that move relative to each other in a fluid environment abound in many settings such as soft contact lenses in eyes, animal joints, and bearings in rotating machinery. Motion is inevitably accompanied by flow and deformation, and raises the question of how these correlate with friction at the interface. A minimal experimental setting, associated with how a cylinder slides and rolls along a soft inclined plane, allows us to see the induction of a self-sustained lift that reduces the friction by nearly an order of magnitude. A simple scaling theory explains our results and suggests a design principle for low-friction interfaces and a partial explanation for phenomena such as reduced wear in animal joints and long-runout landslides. Relative motion between soft wet solids arises in a number of applications in natural and artificial settings, and invariably couples elastic deformation fluid flow. We explore this in a minimal setting by considering a fluid-immersed negatively buoyant cylinder moving along a soft inclined wall. Our experiments show that there is an emergent robust steady-state sliding regime of the cylinder with an effective friction that is significantly reduced relative to that of rigid fluid-lubricated contacts. A simple scaling approach that couples the cylinder-induced flow to substrate deformation allows us to explain the elastohydrodynamic lift that underlies the self-sustained lubricated motion of the cylinder, consistent with recent theoretical predictions. Our results suggest an explanation for a range of effects such as reduced wear in animal joints and long-runout landslides, and can be couched as a design principle for low-friction interfaces.

Cooperative strings and glassy interfaces

Significance According to Philip Anderson, the deepest and most interesting unsolved problem in solid-state physics is probably the glass transition. By extension, this includes the highly debated confinement effects in glassy polymer films. The present article introduces a minimal analytical model, which invokes only the ideas of molecular crowding and string-like cooperative rearrangement, before addressing the key effects of interfaces. The validity and simplicity of the approach make it ideal for application to various systems and geometries, and suggest that dynamics in glass-forming materials might be understood from elementary arguments. We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam–Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel–Fulcher–Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer.

Elastohydrodynamics of a sliding, spinning and sedimenting cylinder near a soft wall

We consider the motion of a fluid-immersed negatively buoyant particle in the vicinity of a thin compressible elastic wall, a situation that arises in a variety of technological and natural settings. We use scaling arguments to establish different regimes of sliding, and complement these estimates using thin-film lubrication dynamics to determine an asymptotic theory for the sedimentation, sliding, and spinning motions of a cylinder. The resulting theory takes the form of three coupled nonlinear singular-differential equations. Numerical integration of the resulting equations confirms our scaling relations and further yields a range of unexpected behaviours. Despite the low-Reynolds feature of the flow, we demonstrate that the particle can spontaneously oscillate when sliding, can generate lift via a Magnus-like effect, can undergo a spin-induced reversal effect, and also shows an unusual sedimentation singularity. Our description also allows us to address a sedimentation-sliding transition that can lead to the particle coasting over very long distances, similar to certain geophysical phenomena. Finally, we show that a small modification of our theory allows to generalize the results to account for additional effects such as wall poroelasticity.

Numerical solutions of thin-film equations for polymer flows

We report on the numerical implementation of thin-film equations that describe the capillary-driven evolution of viscous films, in two-dimensional configurations. After recalling the general forms and features of these equations, we focus on two particular cases inspired by experiments: the leveling of a step at the free surface of a polymer film, and the leveling of a polymer droplet over an identical film. In each case, we first discuss the long-term self-similar regime reached by the numerical solution before comparing it to the experimental profile. The agreement between theory and experiment is excellent, thus providing a versatile probe for nanorheology of viscous liquids in thin-film geometries.Graphical abstract

Beyond Tanner's Law: Crossover between Spreading Regimes of a Viscous Droplet on an Identical Film

We present results on the leveling of polymer microdroplets on thin films prepared from the same material. In particular, we explore the crossover from a droplet spreading on an infinitesimally thin film (Tanners law regime) to that of a droplet leveling on a film thicker than the droplet itself. In both regimes, the droplets excess surface area decreases towards the equilibrium configuration of a flat liquid film, but with a different power law in time. Additionally, the characteristic leveling time depends on molecular properties, the size of the droplet, and the thickness of the underlying film. Flow within the film makes this system fundamentally different from a droplet spreading on a solid surface. We thus develop a theoretical model based on thin film hydrodynamics that quantitatively describes the observed crossover between the two leveling regimes.

Thermoelectric energy recovery at ionic-liquid/electrode interface

A thermally chargeable capacitor containing a binary solution of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide in acetonitrile is electrically charged by applying a temperature gradient to two ideally polarisable electrodes. The corresponding thermoelectric coefficient is -1.7 mV/K for platinum foil electrodes and -0.3 mV/K for nanoporous carbon electrodes. Stored electrical energy is extracted by discharging the capacitor through a resistor. The measured capacitance of the electrode/ionic-liquid interface is 5 μF for each platinum electrode while it becomes four orders of magnitude larger, ≈36 mF, for a single nanoporous carbon electrode. Reproducibility of the effect through repeated charging-discharging cycles under a steady-state temperature gradient demonstrates the robustness of the electrical charging process at the liquid/electrode interface. The acceleration of the charging by convective flows is also observed. This offers the possibility to convert waste-heat into electric energy without exchanging electrons between ions and electrodes, in contrast to what occurs in most thermogalvanic cells.