A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network, and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter.

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a b s t r a c tA network of polymers can imbibe a large quantity of a solvent and swell, resulting in a gel. The swelling process can be markedly influenced by a mechanical load and geometric constraint. When the network, solvent, and mechanical load equilibrate, inside the gel the chemical potential of the solvent is homogeneous, but the concentration of the solvent and the deformation of the network can be inhomogeneous. We use the chemical potential of the solvent and the deformation gradient of the network as the independent variables of the free-energy function, and show that the boundary value problem of the swollen gel is equivalent to that of a hyperelastic solid. We implement this approach in the finite-element package, ABAQUS, and analyze examples of swelling-induced deformation, contact, and bifurcation. Because commercial software like ABAQUS is widely available, this work may provide a powerful tool to study complex phenomena in gels.

When a voltage is applied to a layer of a dielectric elastomer, the layer reduces in thickness and expands in area. A recent experiment has shown that the homogeneous deformation of the layer can be unstable, giving way to an inhomogeneous deformation, such that regions of two kinds coexist in the layer, one being flat and the other wrinkled. To analyze this instability, we construct for a class of model materials, which we call ideal dielectric elastomers, a free-energy function comprising contributions from stretching and polarizing. We show that the free-energy function is typically nonconvex, causing the elastomer to undergo a discontinuous transition from a thick state to a thin state. When the two states coexist in the elastomer, a region of the thin state has a large area and wrinkles when constrained by nearby regions of the thick state. We show that an elastomer described by the Gaussian statistics cannot stabilize the thin state, but a stiffening elastomer near the extension limit can. We further show that the instability can be tuned by the density of cross-links and the state of stress.

Many engineering devices and natural phenomena involve gels that swell under the constraint of hard materials. The constraint causes a field of stress in a gel, and often makes the swelling inhomogeneous even when the gel reaches a state of equilibrium. This paper develops a theory of constrained swelling of a pH-sensitive hydrogel, a network of polymers bearing acidic groups, in equilibrium with an aqueous solution and mechanical forces. The condition of equilibrium is expressed as a variational statement of the inhomogeneous field. A free-energy function accounts for the stretching of the network, mixing of the network with the solution, and dissociation of the acidic groups. Within a Legendre transformation, the condition of equilibrium for the pH-sensitive hydrogel is equivalent to that for a hyperelastic solid. The theory is first used to compare several cases of homogenous swelling: a free gel, a gel attached to a rigid substrate, and a gel confined in three directions. To analyze inhomogeneous swelling, we implement a finite element method in the commercial software ABAQUS, and illustrate the method with a layer of the gel coated on a spherical rigid particle, and a pH-sensitive valve in microfluidics.