764 wileyonlinelibrary.com www.particle-journal.com www.MaterialsViews.comDepending on the volume fraction and interparticle interactions, colloidal suspensions can exhibit a variety of physical states, ranging from fl uids, crystals, and glasses to gels. For microgel particles made of thermoresponsive polymers, both parameters can be tuned using environmental parameters such as temperature and ionic strength, making them excellent systems to experimentally study state transitions in colloidal suspensions. Using a simple two-step synthesis it is shown that the properties of composite microgels, with a fl uorescent latex core and a responsive microgel shell, can be fi nely tuned. With this system the transitions between glass, liquid, and gel states for suspensions composed of a single species are explored. Finally, a suspension of two species of microgels is demonstrated, with different transition temperatures, gels in a sequential manner. Upon increasing temperature a distinct core-sheath structure is formed with a primary gel composed of the species with lowest transition temperature, which acts as a scaffold for the aggregation of the second species.history. Colloidal gels are inherently nonequilibrium structures, which emerge due to diverging time scales during spinodal decomposition of a phase separating suspension. [ 6 ] Any mechanical agitation of such a system causes irreversible changes to both microstructure and mechanical properties. Extensive preshear protocols can be utilized to liquefy colloidal gels, in attempts to create reproducible initial conditions for further experimentation, yet these will typically introduce strong anisotropy into the material. [ 13 ] Ideally, gelation and liquefaction should be reversible and triggerable by means of an environmental parameter, such as temperature. We previously demonstrated that this is possible by using thermoresponsive polymers which exhibit a lower-critical solution temperature (LCST), in which the attractive forces that drive gelation can be turned on and off on demand. [ 14 ] Here, we explore the use of thermoresponsive microgel particles as a controllable system to study colloidal gelation. Microgel particles are crosslinked polymer gel particles of colloidal dimensions swollen with the liquid in which they are dispersed, making them compressible and deformable. The degree of swelling of the microgel is governed by a balance between internal osmotic pressure and elasticity due to crosslinks between the polymer chains. The osmotic pressure depends strongly on the solvent quality, and thus infl uences the equilibrium size of the microgel. For microgels composed of poly( Nisopropylacrylamide), or co-polymers thereof, the solvent quality is temperature dependent due to unfavorable hydrogen bonding between amide groups and the aqueous solvent at temperatures above the LCST. This allows, under specifi c conditions, tuning of the interactions between the microgels from repulsive to attractive; providing the ability to switch between glass, liquid. and gel s...