Robert W. Style

Universal deformation of soft substrates near a contact line and the direct measurement of solid surface stresses

Droplets deform soft substrates near their contact lines. Using confocal microscopy, we measure the deformation of silicone gel substrates due to glycerol and fluorinated-oil droplets for a range of droplet radii and substrate thicknesses. For all droplets, the substrate deformation takes a universal shape close to the contact line that depends on liquid composition, but is independent of droplet size and substrate thickness. This shape is determined by a balance of interfacial tensions at the contact line and provides a novel method for direct determination of the surface stresses of soft substrates. Moreover, we measure the change in contact angle with droplet radius and show that Youngs law fails for small droplets when their radii approach an elastocapillary length scale. For larger droplets the macroscopic contact angle is constant, consistent with Youngs law.

Surface tension and contact with soft elastic solids

The Johnson-Kendall-Roberts theory is the basis of modern contact mechanics. It describes how two deformable objects adhere together, driven by adhesion energy and opposed by elasticity. Here we characterize the indentation of glass particles into soft, silicone substrates using confocal microscopy. We show that, whereas the Johnson-Kendall-Roberts theory holds for particles larger than a critical, elastocapillary lengthscale, it fails for smaller particles. Instead, adhesion of small particles mimics the adsorption of particles at a fluid interface, with a size-independent contact angle between the undeformed surface and the particle given by a generalized version of the Youngs law. A simple theory quantitatively captures this behaviour and explains how solid surface tension dominates elasticity for small-scale indentation of soft materials.

Patterning droplets with durotaxis

Numerous cell types have shown a remarkable ability to detect and move along gradients in stiffness of an underlying substrate—a process known as durotaxis. The mechanisms underlying durotaxis are still unresolved, but generally believed to involve active sensing and locomotion. Here, we show that simple liquid droplets also undergo durotaxis. By modulating substrate stiffness, we obtain fine control of droplet position on soft, flat substrates. Unlike other control mechanisms, droplet durotaxis works without imposing chemical, thermal, electrical, or topographical gradients. We show that droplet durotaxis can be used to create large-scale droplet patterns and is potentially useful for many applications, such as microfluidics, thermal control, and microfabrication.

Stiffening solids with liquid inclusions

Solids embedded with fluid inclusions are intuitively softer than their pure counterparts. But experiments show that when the droplets are small enough, material can become stiffer—highlighting a role for surface tension.

Elastocapillarity: Surface Tension and the Mechanics of Soft Solids

It is widely appreciated that surface tension can dominate the behavior of liquids at small scales. Solids also have surface stresses of a similar magnitude, but they are usually overlooked. However, recent work has shown that these can play a central role in the mechanics of soft solids such as gels. Here, we review this emerging field. We outline the theory of surface stresses, from both mechanical and thermodynamic perspectives, emphasizing the relationship between surface stress and surface energy. We describe a wide range of phenomena at interfaces and contact lines where surface stresses play an important role. We highlight how surface stresses cause dramatic departures from classic theories for wetting (Young–Dupre), adhesion (Johnson–Kendall–Roberts), and composites (Eshelby). A common thread is the importance of the ratio of surface stress to an elastic modulus, which defines a length scale below which surface stresses can dominate.

Solid capillarity: when and how does surface tension deform soft solids?

Soft solids differ from stiff solids in an important way: their surface stresses can drive large deformations. Based on a topical workshop held in the Lorentz Center in Leiden, this Opinion highlights some recent advances in the growing field of solid capillarity and poses key questions for its advancement.

Ice-lens formation and geometrical supercooling in soils and other colloidal materials.

We present a physically intuitive model of ice-lens formation and growth during the freezing of soils and other dense, particulate suspensions. Motivated by experimental evidence, we consider the growth of an ice-filled crack in a freezing soil. At low temperatures, ice in the crack exerts large pressures on the crack walls that will eventually cause the crack to split open. We show that the crack will then propagate across the soil to form a new lens. The process is controlled by two factors: the cohesion of the soil and the geometrical supercooling of the water in the soil, a new concept introduced to measure the energy available to form a new ice lens. When the supercooling exceeds a critical amount (proportional to the cohesive strength of the soil) a new ice lens forms. This condition for ice-lens formation and growth does not appeal to any ad hoc, empirical assumptions, and explains how periodic ice lenses can form with or without the presence of a frozen fringe. The proposed mechanism is in good agreement with experiments, in particular explaining ice-lens pattern formation and surges in heave rate associated with the growth of new lenses. Importantly for systems with no frozen fringe, ice-lens formation and frost heave can be predicted given only the unfrozen properties of the soil. We use our theory to estimate ice-lens growth temperatures obtaining quantitative agreement with the limited experimental data that are currently available. Finally we suggest experiments that might be performed in order to verify this theory in more detail. The theory is generalizable to complex natural-soil scenarios and should therefore be useful in the prediction of macroscopic frost-heave rates.

Wetting and Phase Separation in Soft Adhesion

Significance Modern contact mechanics was originally developed to describe adhesion to relatively stiff materials like rubber, but much softer sticky materials are ubiquitous in biology, medicine, engineering, and everyday consumer products. By studying adhesive contact between compliant gels and rigid objects, we demonstrate that soft materials adhere very differently than their stiffer counterparts. We find that the structure in the region of contact is governed by the same physics that sets the geometry of liquid droplets, even though the material is solid. Furthermore, adhesion can cause the local composition of a soft material to change, thus coupling to its thermodynamic properties. These findings may substantially change our understanding of the mechanics of soft contact. In the classic theory of solid adhesion, surface energy drives deformation to increase contact area whereas bulk elasticity opposes it. Recently, solid surface stress has been shown also to play an important role in opposing deformation of soft materials. This suggests that the contact line in soft adhesion should mimic that of a liquid droplet, with a contact angle determined by surface tensions. Consistent with this hypothesis, we observe a contact angle of a soft silicone substrate on rigid silica spheres that depends on the surface functionalization but not the sphere size. However, to satisfy this wetting condition without a divergent elastic stress, the gel phase separates from its solvent near the contact line. This creates a four-phase contact zone with two additional contact lines hidden below the surface of the substrate. Whereas the geometries of these contact lines are independent of the size of the sphere, the volume of the phase-separated region is not, but rather depends on the indentation volume. These results indicate that theories of adhesion of soft gels need to account for both the compressibility of the gel network and a nonzero surface stress between the gel and its solvent.

Crust formation in drying colloidal suspensions

During the drying of colloidal suspensions, the desiccation process causes the suspension near the air interface to consolidate into a connected porous matrix or crust. Fluid transport in the porous medium is governed by Darcy’s law and the equations of poroelasticity, while the equations of colloid physics govern processes in the suspension. We derive new equations describing this process, including unique boundary conditions coupling the two regions, yielding a moving-boundary model of the concentration and stress profiles during drying. A solution is found for the steady-state growth of a one-dimensional crust during constant evaporation rate from the surface. The solution is used to demonstrate the importance of the system boundary conditions on stress profiles and diffusivity in a drying crust.

Adsorption of soft particles at fluid interfaces

Soft particles can be better emulsifiers than hard particles because they stretch at fluid interfaces. This deformation can increase adsorption energies by orders of magnitude relative to rigid particles. The deformation of a particle at an interface is governed by a competition of bulk elasticity and surface tension. When particles are partially wet by the two liquids, deformation is localized within a material-dependent distance L from the contact line. At the contact line, the particle morphology is given by a balance of surface tensions. When the particle radius R≪L, the particle adopts a lenticular shape identical to that of an adsorbed fluid droplet. Particle deformations can be elastic or plastic, depending on the relative values of the Young modulus, E, and yield stress, σp. When surface tensions favour complete spreading of the particles at the interface, plastic deformation can lead to unusual fried-egg morphologies. When deformable particles have surface properties that are very similar to one liquid phase, adsorption can be extremely sensitive to small changes of their affinity for the other liquid phase. These findings have implications for the adsorption of microgel particles at fluid interfaces and the performance of stimuli-responsive Pickering emulsions.