Particle‐stabilized emulsion gels, or bijels, are used as a general platform for the synthesis of bicontinuous composite materials with various chemistries and morphologies. The method enables the use of ceramics and metals in novel applications where the unique transport and electrochemical properties offered by minimal surface structures may be exploited.

Confocal microscopy and rheology studies of two bijel systems are presented to elucidate relationships between the physicochemical properties of bijels and their ability to be utilized as soft matter templates for materials synthesis. For the first time, the origins of viscoelasticity in these systems are investigated using conventional rheometry and a direct correspondence between the elastic storage modulus, particle loading, and the departure from criticality is observed. Further, the rheological transitions that accompany fluid re‐mixing in bijels are characterized, providing key insights into the synergistic role of interfacial tension and interparticle interactions in mediating their mechanical robustness. Bijels that are predominantly stabilized by interfacial tension are also highly sensitive to gradients in chemical composition and more easily prone to mechanical failure during processing. Despite this increased sensitivity, a modified strategy for processing these more delicate systems is developed and its efficacy is demonstrated by synthesizing a bicontinuous macroporous hydrogel scaffold.

We experimentally characterize the microstructure and rheology of a carefully designed mixture of immiscible fluids and near-neutral-wetting colloidal particles. Particle bridging across two fluid interfaces provides a route to highly stable gel-like emulsions at volume fractions of the dispersed phase well below the random close-packing limit for spheres. We investigate the microstructural origins of this behavior by confocal microscopy and reveal a percolating network of colloidal particles that serves as a cohesive scaffold, bridging together droplets of the dispersed phase. Remarkably, the mixture's salient rheological characteristics are governed predominantly by the solids loading and can be tailored irrespective of the droplet volume fraction. The identification of this rheological hallmark could provide a means toward the improved design of modern products that utilize solid-stabilized interfaces.