Bijel reinforcement by droplet bridging: a route to bicontinuous materials with large domains

Bijels are non-equilibrium solid-stabilized emulsions with bicontinuous arrangement of the constituent fluid phases. These multiphase materials spontaneously form through arrested spinodal decomposition in mixtures of partially miscible liquids and neutrally wetting colloids. Here, we present a new solid-stabilized emulsion with an overall bicontinuous morphology similar to a bijel, but with one continuous phase containing a network of colloid-bridged droplets. This dual morphology is the result of combined spinodal decomposition and nucleation and growth in a binary liquid mixture containing colloidal particles with off-neutral wetting properties and partial affinity for one liquid phase. The rheology of these systems, which we call bridged bijels, is nearly identical to their simple bijel counterparts, with a unique exponential dependence of the zero-shear elastic modulus on the colloid volume fraction. However, partitioning of the colloids between the spinodal surface and the fluid domains delays the onset of structural arrest, providing access to domain sizes much larger than available in simple bijels without loss of mechanical stability. This ability greatly expands the potential technological applications of these unique materials. In addition, our findings reveal new strategies for tuning the rheology of bijels and outline new directions for future fundamental research on this unique class of soft materials.