Microgel Assembly: From Bulk Phases to Interfaces

This chapter provides a comprehensive overview of microgel assembly across bulk phases and interfaces, emphasizing their unique structural and stimuli-responsive properties. We first discuss self-assembly mechanisms of microgels in aqueous and non-aqueous bulk phases, driven by a range of interactions. The focus then shifts to microgel interfacial assembly at water–air, oil–water, and unconventional interfaces (e.g. water–water and oil–oil), highlighting how microgel softness, architecture, and environmental factors (temperature, pH, and surface pressure) influence interfacial patterns and stability. Additionally, the role of microgels in stabilizing biphasic systems (e.g. Pickering foams and emulsions) is demonstrated, alongside regulatory mechanisms governing their interfacial assembly structures. Furthermore, we explore promising applications leveraging microgel assemblies at the interface, including food three-dimensional printing, interfacial catalysis, smart colloidosomes, and programmable release systems. The interplay between microgel design, assembly behavior, and functionality underscores their potential in materials science, biomedicine, and industrial processes.