Effect of Charge Groups Immobilized in Hydrogel Microspheres during the Evaporation of Aqueous Sessile Droplets

In contrast to conventional dispersions of solid microspheres, dilute dispersions containing soft hydrogel microspheres (microgels) exhibit unique drying behavior due to their selective adsorption at the air/water interface of sessile droplets. So far, the impact of the size, chemical composition, and softness (degree of cross-linking) of microgels has been investigated. In the present study, we present the impact of charged groups introduced in the microgels on the adsorption and assembly behavior of these microgels at the air/water interface using a series of microgels with different amounts and distribution of charged groups. A series of experiments under different conditions (pH value and ionic strength) afforded information that clarified the adsorption, interpenetration, and deformation behavior of such charged microgels at the air/water interface. The results indicate that the adsorption and the deformation of charged microgels at the air/water interface are suppressed by the presence of charged groups. Moreover, charged microgels adsorbed at the interface are more dynamic and not highly entangled with each other; i.e., even though the more dynamic charged microgels are arranged at the interface, these arranged structures are disrupted upon transferring onto the solid substrates. Our findings of this study can be expected to promote the further development of applications, e.g., foams and emulsions stabilized by microgels, that crucially requires an in-depth understanding of the adsorption behavior of charged microgels at the air/water interface such as coatings.