Elastic microphase separation produces robust bicontinuous materials.

Bicontinuous microstructures are essential to the function of diverse natural and synthetic systems. Their synthesis has been based on two approaches: arrested phase separation or self-assembly of block copolymers. The former is attractive for its chemical simplicity and the latter, for its thermodynamic robustness. Here we introduce elastic microphase separation (EMPS) as an alternative approach to make bicontinuous microstructures. Conceptually, EMPS balances the molecular-scale forces that drive demixing with large-scale elasticity to encode a thermodynamic length scale. This process features a continuous phase transition, reversible without hysteresis. Practically, EMPS is triggered by simply supersaturating an elastomeric matrix with a liquid, resulting in uniform bicontinuous materials with a well-defined microscopic length scale tuned by the matrix stiffness. The versatility of EMPS is further demonstrated by fabricating bicontinuous materials with superior mechanical properties and controlled anisotropy and microstructural gradients. Overall, EMPS presents a robust alternative for the bulk fabrication of homogeneous bicontinuous materials.

Stress accumulation by confined ice in a temperature gradient.

When materials freeze, they often undergo damage due to ice growth. Although this damage is commonly ascribed to the volumetric expansion of water upon freezing, it is usually driven by the flow of water toward growing ice crystals that feeds their growth. The freezing of this additional water can cause a large buildup of stress. Here, we demonstrate a technique for characterizing this stress buildup with unprecedented spatial resolution. We create a stable ice-water interface in a controlled temperature gradient and measure the deformation of the confining boundary. Analysis of the deformation field reveals stresses applied to the boundary with [Formula: see text](micrometers) spatial resolution. Globally, stresses increase steadily over time as liquid water is transported to more deeply undercooled regions. Locally, stresses increase until ice growth is stalled by the confining stresses. Importantly, we find a strong localization of stresses, which significantly increases the likelihood of damage caused by the presence of ice, even in apparently benign freezing situations. Ultimately, the limiting stress that the ice exerts is proportional to the local undercooling, in accordance with the Clapeyron equation, which describes the equilibrium between a stressed solid and its melt. Our results are closely connected to the condensation pressure during liquid-liquid phase separation and the crystallization pressure for growing crystals. Thus, they are highly relevant in fields ranging from cryopreservation and frost heave to food science, rock weathering, and art conservation.

Polycrystallinity Enhances Stress Buildup around Ice.

Damage caused by freezing wet, porous materials is a widespread problem but is hard to predict or control. Here, we show that polycrystallinity significantly speeds up the stress buildup process that underpins this damage. Unfrozen water in grain-boundary grooves feeds ice growth at temperatures below the freezing temperature, leading to fast stress buildup. These stresses can build up to levels that can easily break many brittle materials. The dynamics of the process are very variable, which we ascribe to local differences in ice-grain orientation and to the surprising mobility of many grooves-which further accelerates stress buildup. Our Letter will help understand how freezing damage occurs and in developing accurate models and effective damage-mitigation strategies.

Surface Passivation Method for the Super-repellence of Aqueous Macromolecular Condensates.

Solutions of macromolecules can undergo liquid-liquid phase separation to form droplets with ultralow surface tension. Droplets with such low surface tension wet and spread over common surfaces such as test tubes and microscope slides, complicating in vitro experiments. The development of a universal super-repellent surface for macromolecular droplets has remained elusive because their ultralow surface tension requires low surface energies. Furthermore, the nonwetting of droplets containing proteins poses additional challenges because the surface must remain inert to a wide range of chemistries presented by the various amino acid side chains at the droplet surface. Here, we present a method to coat microscope slides with a thin transparent hydrogel that exhibits complete dewetting (contact angles θ ≈ 180°) and minimal pinning of phase-separated droplets in aqueous solution. The hydrogel is based on a swollen matrix of chemically cross-linked polyethylene glycol diacrylate of molecular weight 12 kDa (PEGDA), and can be prepared with basic chemistry laboratory equipment. The PEGDA hydrogel is a powerful tool for in vitro studies of weak interactions, dynamics, and the internal organization of phase-separated droplets in aqueous solutions.

Strain stiffening elastomers with swelling inclusions.

Inhomogeneously swollen elastomers are an emergent class of materials, comprising elastic matrices with inclusion phases in the form of microgel particles or osmolytes. Inclusion phases can undergo osmotically driven swelling and deswelling over orders of magnitude. In the swollen state, the inclusions typically have negligible Young's modulus, and the matrix is strongly deformed. In that regime, the effective mechanical properties of the composite are governed by the matrix. Laying the groundwork for a generic analysis of inhomogeneously swollen elastomers, we develop a model based on incremental mean-field homogenization of a hyperelastic matrix. The framework allows for the computation of the macroscopic effective stiffness for arbitrary hyperelastic matrix materials. For an in-depth quantification of the local effective stiffness, we extend the concept of elastic stiffness maps to incompressible materials. For strain-stiffening materials, stiffness maps in the swollen state highlight pronounced radial stiffening with a non-monotonic change in stiffness in the hoop direction. Stiffening characteristics are sensitive to the form of constitutive models, which may be exploited in the design of hydrated actuators, soft composites and metamaterials. For validation, we apply this framework to a Yeoh material, and compare to recently published data. Model predictions agree well with experimental data on elastomers with highly swollen embedded microgel particles. We identify three distinct regimes related to an increasing degree of particle swelling: first, an initial decrease in composite stiffness is attributed to particle softening upon liquid intake. Second, dilute particle swelling leads to matrix stiffening dominating over particle softening, resulting in an increase in composite stiffness. Third, for swelling degrees beyond the dilute limit, particle interactions dominate further matrix stiffening.

Hydroelastomers: soft, tough, highly swelling composites.

Inspired by the cellular design of plant tissue, we present an approach to make versatile, tough, highly water-swelling composites. We embed highly swelling hydrogel particles inside tough, water-permeable, elastomeric matrices. The resulting composites, which we call hydroelastomers, combine the properties of their parent phases. From their hydrogel component, the composites inherit the ability to highly swell in water. From the elastomeric component, the composites inherit excellent stretchability and fracture toughness, while showing little softening as they swell. Indeed, the fracture properties of the composite match those of the best-performing, tough hydrogels, exhibiting fracture energies of up to 10 kJ m-2. Our composites are straightforward to fabricate, based on widely-available materials, and can easily be molded or extruded to form shapes with complex swelling geometries. Furthermore, there is a large design space available for making hydroelastomers, since one can use any hydrogel as the dispersed phase in the composite, including hydrogels with stimuli-responsiveness. These features make hydroelastomers excellent candidates for use in soft robotics and swelling-based actuation, or as shape-morphing materials, while also being useful as hydrogel replacements in other fields.

Forming Anisotropic Crystal Composites: Assessing the Mechanical Translation of Gel Network Anisotropy to Calcite Crystal Form.

The promise of crystal composites with direction-specific properties is an attractive prospect for diverse applications; however, synthetic strategies for realizing such composites remain elusive. Here, we demonstrate that anisotropic agarose gel networks can mechanically "mold" calcite crystal growth, yielding anisotropically structured, single-crystal composites. Drying and rehydration of agarose gel films result in the affine deformation of their fibrous networks to yield fiber alignment parallel to the drying plane. Precipitation of calcium carbonate within these anisotropic networks results in the formation of calcite crystal composite disks oriented parallel to the fibers. The morphology of the disks, revealed by nanocomputed tomography imaging, evolves with time and can be described by linear-elastic fracture mechanics theory, which depends on the ratio between the length of the crystal and the elastoadhesive length of the gel. Precipitation of calcite in uniaxially deformed agarose gel cylinders results in the formation of rice-grain-shaped crystals, suggesting the broad applicability of the approach. These results demonstrate how the anisotropy of compliant networks can translate into the desired crystal composite morphologies. This work highlights the important role organic matrices can play in mechanically "molding" biominerals and provides an exciting platform for fabricating crystal composites with direction-specific and emergent functional properties.

Surface Tension and the Strain-Dependent Topography of Soft Solids.

When stretched in one direction, most solids shrink in the transverse directions. In soft silicone gels, however, we observe that small-scale topographical features grow upon stretching. A quantitative analysis of the topography shows that this counterintuitive response is nearly linear, allowing us to tackle it through a small-strain analysis. We find that the surprising increase of small-scale topography with stretch is due to a delicate interplay of the bulk and surface responses to strain. Specifically, we find that surface tension changes as the material is deformed. This response is expected on general grounds for solid materials, but challenges the standard description of gel and elastomer surfaces.

Droplets Sit and Slide Anisotropically on Soft, Stretched Substrates.

Anisotropically wetting substrates enable useful control of droplet behavior across a range of applications. Usually, these involve chemically or physically patterning the substrate surface, or applying gradients in properties like temperature or electrical field. Here, we show that a flat, stretched, uniform soft substrate also exhibits asymmetric wetting, both in terms of how droplets slide and in their static shape. Droplet dynamics are strongly affected by stretch: glycerol droplets on silicone substrates with a 23% stretch slide 67% faster in the direction parallel to the applied stretch than in the perpendicular direction. Contrary to classical wetting theory, static droplets in equilibrium appear elongated, oriented parallel to the stretch direction. Both effects arise from droplet-induced deformations of the substrate near the contact line.

Surface tensiometry of phase separated protein and polymer droplets by the sessile drop method.

Phase separated macromolecules play essential roles in many biological and synthetic systems. Physical characterization of these systems can be challenging because of limited sample volumes, particularly for phase-separated proteins. Here, we demonstrate that a classic method for measuring the surface tension of liquid droplets, based on the analysis of the shape of a sessile droplet, can be effectively scaled down to measure the interfacial tension between a macromolecule-rich droplet phase and its co-existing macromolecule-poor continuous phase. The connection between droplet shape and surface tension relies on the density difference between the droplet and its surroundings. This can be determined with small sample volumes in the same setup by measuring the droplet sedimentation velocity. An interactive MATLAB script for extracting the capillary length from a droplet image is included in the ESI.

Structural color from solid-state polymerization-induced phase separation.

Structural colors are produced by wavelength-dependent scattering of light from nanostructures. While living organisms often exploit phase separation to directly assemble structurally colored materials from macromolecules, synthetic structural colors are typically produced in a two-step process involving the sequential synthesis and assembly of building blocks. Phase separation is attractive for its simplicity, but applications are limited due to a lack of robust methods for its control. A central challenge is to arrest phase separation at the desired length scale. Here, we show that solid-state polymerization-induced phase separation can produce stable structures at optical length scales. In this process, a polymeric solid is swollen and softened with a second monomer. During its polymerization, the two polymers become immiscible and phase separate. As free monomer is depleted, the host matrix resolidifies and arrests coarsening. The resulting polymeric composites have a blue or white appearance. We compare these biomimetic nanostructures to those in structurally-colored feather barbs, and demonstrate the flexibility of this approach by producing structural color in filaments and large sheets.

Viscoelastic and Poroelastic Relaxations of Soft Solid Surfaces.

Understanding surface mechanics of soft solids, such as soft polymeric gels, is crucial in many engineering processes, such as dynamic wetting and adhesive failure. In these situations, a combination of capillary and elastic forces drives the motion, which is balanced by dissipative mechanisms to determine the rate. While shear rheology (i.e., viscoelasticity) has long been assumed to dominate the dissipation, recent works have suggested that compressibility effects (i.e., poroelasticity) could play roles in swollen networks. We use fast interferometric imaging to quantify the relaxation of surface deformations due to a displaced contact line. By systematically measuring the profiles at different time and length scales, we experimentally observe a crossover from viscoelastic to poroelastic surface relaxations.

Wrapping of Microparticles by Floppy Lipid Vesicles.

Lipid membranes, the barrier defining living cells and many of their subcompartments, bind to a wide variety of nano- and micrometer sized objects. In the presence of strong adhesive forces, membranes can strongly deform and wrap the particles, an essential step in crossing the membrane for a variety of healthy and disease-related processes. A large body of theoretical and numerical work has focused on identifying the physical properties that underly wrapping. Using a model system of micron-sized colloidal particles and giant unilamellar lipid vesicles with tunable adhesive forces, we measure a wrapping phase diagram and make quantitative comparisons to theoretical models. Our data are consistent with a model of membrane-particle interactions accounting for the adhesive energy per unit area, membrane bending rigidity, particle size, and vesicle radius.

Switchable adhesion of soft composites induced by a magnetic field.

Switchable adhesives have the potential to improve the manufacturing and recycling of parts, and to enable new modes of motility for soft robots. Here, we demonstrate magnetically-switchable adhesion of a two-phase composite to non-magnetic objects. The composite's continuous phase is a silicone elastomer, and the dispersed phase is a magneto-rheological fluid. The composite is simple to prepare, and to mold into different shapes. When a magnetic field is applied, the magneto-rheological fluid develops a yield stress, which dramatically enhances the composite's adhesive properties. We demonstrate up to a nine-fold increase of the pull-off force of non-magnetic objects in the presence of a 250 mT field.

Elastic stresses reverse Ostwald ripening.

When liquid droplets nucleate and grow in a polymer network, compressive stresses can significantly increase their internal pressure, reaching values that far exceed the Laplace pressure. When droplets have grown in a polymer network with a stiffness gradient, droplets in relatively stiff regions of the network tend to dissolve, favoring growth of droplets in softer regions. Here, we show that this elastic ripening can be strong enough to reverse the direction of Ostwald ripening: large droplets can shrink to feed the growth of smaller ones. To numerically model these experiments, we generalize the theory of elastic ripening to account for gradients in solubility alongside gradients in mechanical stiffness.

Effects of strain-dependent surface stress on the adhesive contact of a rigid sphere to a compliant substrate.

Recent experiments have reported that the surface stress of soft elastic solids can increase rapidly with surface strain. For example, when a small hard sphere in adhesive contact with a soft silicone gel is slowly retracted from its rest position, it was found that the retraction force versus displacement relation cannot be explained either by the Johnson-Kendall-Roberts (JKR) theory or a recent indentation theory based on an isotropic surface stress that is independent of surface strain. In this paper, we address this problem using a finite element method to simulate the retraction process. Our numerical model does not have the restrictions of the aforementioned theories; that is, it can handle large nonlinear elastic deformation as well as a surface-strain-dependent surface stress. Our simulation is in good agreement with experimental force versus displacement data with no fitting parameters. Therefore, our results lend further support to the claim that significant strain-dependent surface stresses can occur in simple soft elastic gels. However, significant challenges remain in the reconciliation of theory and experiments, particularly regarding the geometry of the contact and substrate deformation.

Singular dynamics in the failure of soft adhesive contacts.

We characterize the mechanical recovery of compliant silicone gels following adhesive contact failure. We establish broad, stable adhesive contacts between rigid microspheres and soft gels, then stretch the gels to large deformations by pulling quasi-statically on the contact. Eventually, the adhesive contact begins to fail, and ultimately slides to a final contact point on the bottom of the sphere. Immediately after detachment, the gel recoils quickly with a self-similar surface profile that evolves as a power law in time, suggesting that the adhesive detachment point is singular. The singular dynamics we observe are consistent with a relaxation process driven by surface stress and slowed by viscous flow through the porous, elastic network of the gel. Our results emphasize the importance of accounting for both the liquid and solid phases of gels in understanding their mechanics, especially under extreme deformation.

The mechanical equilibrium of soft solids with surface elasticity.

Recent experiments have shown that surface stresses in soft materials can have a significant strain-dependence. Here we explore the implications of this surface elasticity to show how, and when, we expect it to arise. We develop the appropriate boundary condition, showing that it simplifies significantly in certain cases. We show that surface elasticity's main role is to stiffen a solid surface's response to in-plane tractions, in particular at length-scales smaller than a characteristic elastocapillary length. We also investigate how surface elasticity affects the Green's-function problem of a line force on a flat, incompressible, linear-elastic substrate. There are significant changes to this solution, especially in that the well-known displacement singularity is regularised. This raises interesting implications for soft phenomena like wetting contact lines, adhesion and friction. Finally, we discuss open questions, future directions, and close ties with existing fields of research.

Surface elastic constants of a soft solid.

Solid interfaces have intrinsic elasticity. However, in most experiments, this is obscured by bulk stresses. Through microscopic observations of the contact-line geometry of a partially wetting droplet on an anisotropically stretched substrate, we measure two surface-elastic constants that quantify the linear dependence of the surface stress of a soft polymer gel on its strain. With these two parameters, one can predict surface stresses for general deformations of the material in the linear-elastic limit.

The contact mechanics challenge: tribology meets soft matter.

In the fall of 2015, Martin Müser suggested a Contact Mechanics Challenge for the Tribology community. The challenge was an ambitious effort to compare a wide variety of theoretical and computational contact-mechanics approaches, and involved researchers voluntarily tackling the same hypothetical contact problem. The result is an impressive collection of innovative approaches - including a surprise experimental effort - that highlight the continuing importance of surface contact mechanics and the challenges of solving these large-scale problems. Here, we describe how the Contact Mechanics Challenge also reveals exciting opportunities for the Soft Matter community to engage intensely with classical and emerging problems in tribology, surface science, and contact mechanics.