Search

We report on the frictional properties of thin ($\approx \mu m$) poly(dimethylacrylamide) hydrogel films within contacts with spherical silica probes. In order to focus on the contribution to friction of interfacial dissipation, a dedicated rotational setup is designed which allows to suppress poroelastic flows while ensuring an uniform velocity field at the sliding interface. The physical-chemistry of the interface is varied from the grafting of various silanes on the silica probes. Remarkably, we identify a velocity range in which the average frictional stress systematically varies with the logarithm of the sliding velocity. This dependency is found to be sensitive to the physical-chemistry of the silica surfaces. Experimental observations are discussed in the light of a molecular model where friction arises from thermally activated adsorption of polymer chains at the sliding interface, their elastic stretching and subsequent desorption. From this theoretical description, our experimental data provide us with adhesion energies and characteristic times for molecular adsorption that are found consistent with the physico-chemistry of the chemically-modified silica surfaces.

Emulsion droplets of silicone oil (PDMS) are widely used as antifoaming agents but, in the case of non-aqueous foams, the mechanisms responsible for the bursting of the films separating the bubbles remain unclear. We consider a ternary non-aqueous liquid mixture in which PDMS-rich microdroplets are formed by spontaneous emulsification. In order to quantitatively assess the effect of the emulsified microdroplets, we measure the lifetime of sub-micrometer-thick suspended films of these emulsions as well as the time variations of their thickness profiles. We observe that a droplet entering the film reduces its lifetime by inducing a local and fast thinning. In most cases, we ascribe it to the spreading of the drop at one of the film interface with air, which drags the underlying liquid and causes eventually the film to burst rapidly. We explain why, despite slower spreading, more viscous droplets cause films to burst more efficiently. More rarely, microdroplets may bridge the two interfaces of the film, resulting in an even more efficient bursting of the film that we explain.

Nanometer-thick supported lms of polymer melts spontaneously form and spread around sessile droplets that are deposited on oxidized silicon wafers. At steady state, the lms become dense and adopt a uniform thickness which is equal to twice the gyration radius of the free polymer. Remarkably, this law applies to a wide variety of melts and does not depend on the polymer chemistry nor on the surface state (oxide layer thickness, temperature, presence of water adsorbed, etc.). We show that existing theoretical descriptions cannot reproduce this experimental result. Conversely, the evolution toward this equilibrium state witnesses the specicity of the interactions at stake in these conned polymer lms. The chains spreading dynamics can be modeled by taking into account both the polymer/surface friction and the polymer/polymer friction., Comment: Macromolecules, inPress

We report on the delamination of thin ($\approx \mu$m) hydrogel films grafted to silicon substrates under the action of swelling stresses. Poly(dimetylacrylamide) (PDMA) films are synthesized by simultaneously cross-linking and grafting preformed polymer chains onto the silicon substrate using a thiol-ene reaction. The grafting density at the film/substrate interface is tuned by varying the surface density of reactive thiol-silane groups on the silicon substrate. Delamination of the films from well controlled line defects with low adhesion is monitored under a humid water vapor flow ensuring full saturation of the polymer network. A propagating delamination of the film is observed under the action of differential swelling stresses at the debonding front. A threshold thickness for the onset of this delamination is evidenced which is increasing with grafting density while the debonding velocity is also observed to decrease with an increase in grafting density. These observations are discussed within the framework of a nonlinear fracture mechanics model which assumes that the driving force for crack propagation is the difference between the swelling state of the bonded and delaminated parts of the film. Using this model, the threshold energy for crack initiation was determined from the measured threshold thickness and discussed in relation to the surface density of reactive thiol groups on the substrate.

When a drop laden with solid particles and suspended in a liquid passes through a narrow pore, its interface experiences strong shear and elongation, and the raft of particles may accumulate toward the back of the drop. Using well controlled formulations of Pickering drops driven at set pressure, we determine the two conditions for which solid particles are expelled from the oil-water interface after a Pickering drop passes a converging-diverging pore: (i) particles accumulation at the rear of the drop is such that surface pressure builds-up at the interface. (ii) Surface pressure relaxation by buckling is impaired by geometrical constraints. These two conditions are rationalized using three non dimensional numbers: the capillary number, the particle to pore size ratio, and the drop to particle size ratio, which allow to account for the viscous shear at the interface, the stability of the lubricating film between the pore wall and the drop, the drag on the raft of particles adsorbed at the interface, and its mechanical behaviour.

We report on the transient frictional response of contacts between a rigid spherical glass probe and a micrometer-thick poly(dimethylacrylamide) hydrogel film grafted onto a glass substrate when a lateral relative motion is applied to the contact initially at rest. From dedicated experiments with \textit{in situ} contact visualization, both the friction force and the contact size are observed to vary well beyond the occurrence of a full sliding condition at the contact interface. Depending on the imposed velocity and on the static contact time before the motion is initiated, either an overshoot or an undershoot in the friction force is observed. These observations are rationalized by considering that the transient is predominantly driven by the flow of water within the stressed hydrogel networks. From the development of a poroelastic contact model using a thin film approximation, we provide a theoretical description of the main features of the transient. We especially justify the experimental observation that the relaxation of friction force $F_t(t)$ toward steady state is uniquely dictated by the time-dependence of the contact radius $a(t)$, independently on the sliding velocity and on the applied normal load.

We report on the frictional behaviour of thin poly(dimethylacrylamide) (PDMA) hydrogels films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and applied normal loads with the contact fully immersed in water. In addition to friction force measurements, a novel optical set-up is designed to image the shape of the contact under steady-state sliding. The velocity-dependence of both friction force $F_t$ and contact shape is found to be controlled by a P\'eclet number Pe defined as the ratio of the time $\tau$ needed to drain the water out of the contact region to a contact time $a/v$, where $v$ is the sliding velocity and $a$ is the contact radius. When Pe<1, the equilibrium circular contact achieved under static normal indentation remains unchanged during sliding. Conversely, for Pe>1, a decrease in the contact area is observed together with the development of a contact asymmetry when the sliding velocity is increased. A maximum in $F_t$ is also observed at Pe~$\approx$~1. These experimental observations are discussed in the light of a poroelastic contact model based on a thin film approximation. This model indicates that the observed changes in contact geometry are due to the development of a pore pressure imbalance when Pe>1. An order of magnitude estimate of the friction force and its dependence on normal load and velocity is also provided under the assumption that most of the frictional energy is dissipated by poroelastic flow at the leading and trailing edges of the sliding contact.

We report on the poroelastic indentation response of hydrogel thin films geometrically confined within contacts with rigid spherical probes of radii in the millimeter range. Poly(PEGMA) (poly(ethylene glycol)) methyl ether methacrylate), poly(DMA) (dimethylacrylamide) and poly(NIPAM) (\textit{N}-isopropylacrylamide) gel films with thickness less than 15 $\mu$m were grafted onto glass substrates using a thiol-ene click chemistry route. Changes in the indentation depth under constant applied load were monitored over time as a function of the film thickness and the radius of curvature of the probe using an interferometric method. In addition, shear properties of the indented films were measured using a lateral contact method. In the case of poly(PEGMA) films, we show that poroelastic indentation behavior is adequately described within the framework of an approximate contact model derived within the limits of confined contact geometries. This model provides simple scaling laws for the characteristic poroelastic time and the equilibrium indentation depth. Conversely, deviations from this model are evidenced for poly(DMA) and poly(NIPAM) films. From lateral contact experiments, these deviations are found to result from strong changes in the shear properties as a result of glass transition (poly(DMA)) or phase separation (poly(NIPAM)) phenomena induced by the drainage of the confined films squeezed between the rigid substrates.

We measure the flow of water through mixed packings of glass spheres and soft swellable hydrogel grains, at constant sample volume. Permeability values are obtained at constant sample volume and at porosities smaller than random close packing, for different glass bead diameters $D$ and for variable gel grain diameter $d$, as controlled by the salinity of the water. The gel content is also varied. We find that the permeability decays exponentially in $n(D/d)^b$ where $n=N_{gel}/N_{glass}$ is the gel to glass bead number ratio and $b$ is approximately 3. Therefore, flow properties are determined by the volume fraction of gel beads. A simple model based on the porosity of overlapping spheres is used to account for these observations.

When a liquid drops impinges a hydrophobic rough surface it can either bounce off the surface (fakir droplets) or be impaled and strongly stuck on it (Wenzel droplets). The analysis of drop impact and quasi static ''loading'' experiments on model microfabricated surfaces allows to clearly identify the forces hindering the impalement transitions. A simple semi-quantitative model is proposed to account for the observed relation between the surface topography and the robustness of fakir non-wetting states. Motivated by potential applications in microfluidics and in the fabrication of self cleaning surfaces, we finally propose some guidelines to design robust superhydrophobic surfaces., Comment: 7 pages, 5 figures