Swelling induced debonding of thin hydrogel films grafted on silicon substrates.

We report on the delamination of thin (≈µm) 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.

Transient sliding of thin hydrogel films: the role of poroelasticity.

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 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 Ft(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.

Swelling Dynamics of Surface-Attached Hydrogel Thin Films in Vapor Flows.

Hydrogel coatings absorb water vapor, or other solvents, and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower than the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied cross-links density, and varied affinity for water, we were able to determine the effect of the film hygroscopy on the dynamics of swelling of the film. These experimental results are accounted for by a diffusion-advection model that is supplemented with a boundary condition at the hydrogel surface: we show that the latter can be determined from the equilibrium sorption isotherms of the polymer films. Altogether, this paper offers a predictive tool for the swelling kinetics of any hydrophilic hydrogel thin film.

Friction of Poroelastic Contacts with Thin Hydrogel Films.

We report on the frictional behavior of thin poly(dimethylacrylamide) hydrogel films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and normal loads applied with the contact fully immersed in water. In addition to friction force measurements, a novel optical setup is designed to image the shape of the contact under steady-state sliding. The velocity dependence of both friction force Ft and contact shape is found to be controlled by a Péclet number, Pe, defined as the ratio of the time τ 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 Ft is also observed at Pe ≈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 are 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.

Role of uncrosslinked chains in droplets dynamics on silicone elastomers.

We report an unexpected behavior in wetting dynamics on soft silicone substrates: the dynamics of aqueous droplets deposited on vertical plates of such elastomers exhibits two successive speed regimes. This macroscopic observation is found to be closely related to microscopic phenomena occurring at the scale of the polymer network: we show that uncrosslinked chains found in most widely used commercial silicone elastomers are responsible for this surprising behavior. A direct visualization of the uncrosslinked oligomers collected by water droplets is performed, evidencing that a capillarity-induced phase separation occurs: uncrosslinked oligomers are extracted from the silicone elastomer network by the water-glycerol mixture droplet. The sharp speed change is shown to coincide with an abrupt transition in surface tension of the droplets, when a critical surface concentration in uncrosslinked oligomer chains is reached. We infer that a droplet shifts to a second regime with a faster speed when it is completely covered with a homogeneous oil film.

Contact of a spherical probe with a stretched rubber substrate.

We report on a theoretical and experimental investigation of the normal contact of stretched neo-Hookean substrates with rigid spherical probes. Starting from a published formulation of surface Green's function for incremental displacements on a prestretched, neo-Hookean, substrate [J. Mech. Phys. Solids 56, 2957 (2008)JMPSA80022-509610.1016/j.jmps.2008.07.002], a model is derived for both adhesive and nonadhesive contacts. The shape of the elliptical contact area together with the contact load and the contact stiffness are predicted as a function of the in-plane stretch ratios λ_{x} and λ_{y} of the substrate. The validity of this model is assessed by contact experiments carried out using an uniaxally stretched silicone rubber. For stretch ratio below about 1.25, a good agreement is observed between theory and experiments. Above this threshold, some deviations from the theoretical predictions are induced as a result of the departure of the mechanical response of the silicone rubber from the neo-Hokeean description embedded in the model.

Soft Lithography Using Nectar Droplets.

In spite of significant advances in replication technologies, methods to produce well-defined three-dimensional structures are still at its infancy. Such a limitation would be evident if we were to produce a large array of simple and, especially, compound convex lenses, also guaranteeing that their surfaces would be molecularly smooth. Here, we report a novel method to produce such structures by cloning the 3D shape of nectar drops, found widely in nature, using conventional soft lithography.The elementary process involves transfer of a thin patch of the sugar solution coated on a glass slide onto a hydrophobic substrate on which this patch evolves into a microdroplet. Upon the absorption of water vapor, such a microdroplet grows linearly with time, and its final size can be controlled by varying its exposure time to water vapor. At any stage of the evolution of the size of the drop, its shape can be cloned onto a soft elastomer by following the well-known methods of molding and cross-linking the same. A unique new science that emerges in our attempt to understand the transfer of the sugar patch and its evolution to a spherical drop is the elucidation of the mechanics underlying the contact of a deformable sphere against a solid support intervening a thin liquid film. A unique aspect of this work is to demonstrate that higher level structures can also be generated by transferring even smaller nucleation sites on the surface of the primary lenses and then allowing them to grow by absorption of water vapor. What results at the end is either a well-controlled distribution of smooth hemispherical lenses or compound structures that could have potential applications in the fundamental studies of contact mechanics, wettability, and even in optics.

Friction of viscoelastic elastomers with rough surfaces under torsional contact conditions.

Frictional properties of contacts between a smooth viscoelastic rubber and rigid surfaces are investigated using a torsional contact configuration where a glass lens is continuously rotated on the rubber surface. From the inversion of the displacement field measured at the surface of the rubber, spatially resolved values of the steady state frictional shear stress are determined within the nonhomogeneous pressure and velocity fields of the contact. For contacts with a smooth lens, a velocity-dependent but pressure-independent local shear stress is retrieved from the inversion. On the other hand, the local shear stress is found to depend on both velocity and applied contact pressure when a randomly rough (sand-blasted) glass lens is rubbed against the rubber surface. As a result of changes in the density of microasperity contacts, the amount of light transmitted by the transparent multicontact interface is observed to vary locally as a function of both contact pressure and sliding velocity. Under the assumption that the intensity of light transmitted by the rough interface is proportional to the proportion of area into contact, it is found that the local frictional stress can be expressed experimentally as the product of a purely velocity-dependent term, k(v), by a term representing the pressure and velocity dependence of the actual contact area, A/A(0). A comparison between k(v) and the frictional shear stress of smooth contacts suggests that nanometer scale dissipative processes occurring at the interface predominate over viscoelastic dissipation at microasperity scale.

Contact compliance effects in the frictional response of bioinspired fibrillar adhesives.

The shear failure and friction mechanisms of bioinspired adhesives consisting of elastomer arrays of microfibres terminated by mushroom-shaped tips are investigated in contact with a rigid lens. In order to reveal the interplay between the vertical and lateral loading directions, experiments are carried out using a custom friction set-up in which normal stiffness can be made either high or low when compared with the stiffness of the contact between the fibrillar adhesive and the lens. Using in situ contact imaging, the shear failure of the adhesive is found to involve two successive mechanisms: (i) cavitation and peeling at the contact interface between the mushroom-shaped fibre tip endings and the lens; and (ii) side re-adhesion of the fibre's stem to the lens. The extent of these mechanisms and their implications regarding static friction forces is found to depend on the crosstalk between the normal and lateral loading directions that can result in contact instabilities associated with fibre buckling. In addition, the effects of the viscoelastic behaviour of the polyurethane material on the rate dependence of the shear response of the adhesive are accounted for.

Friction and shear fracture of an adhesive contact under torsion.

The shear failure or stiction of an adhesive contact between a poly(dimethylsiloxane) (PDMS) rubber and a glass lens has been investigated using a torsional contact configuration. As compared to linear sliding, torsion presents the advantage of inducing a shear failure under a pure mode III condition, while preserving the cylindrical symmetry of the contact. The surface of the transparent PDMS substrate was marked using a network of dots in order to monitor continuously the in-plane surface displacements during the stiction process. Using a previously developed inversion procedure (A. Chateauminois and C. Fretigny, Eur. Phys. J. E 27, 221 (2008)), the corresponding surface shear stress distributions were obtained from the displacement fields. Stiction was found to involve the progressive shrinkage of a central adhesive zone surrounded by an annular microslip region. Adhesion effects were especially evidenced from a stress overshoot at the boundary of the adhesive zone. The experimental data were analysis using an extension to torsional contact of the Maugis-Dugdale approach's to adhesive contacts which takes into account frictional effects. This model allowed to extract an effective adhesion energy in the presence of friction, which dependence on kinetics effect is briefly discussed.