Tuning the particle-surface interactions in aqueous solutions by soft microgel particles.

Due to the softness and deformability, interaction between colloidal surfaces induced by soft particles varies in a more complex way than for solid particles and thus has attracted much attention in recent years. In the present study, we use total internal reflection microscopy (TIRM) to directly measure the interaction between polystyrene (PS) microparticles and a flat glass surface in a poly(N-isopropylacrylamide) (PNIPAM) microgel dispersion with concentration varying from dilute (0.1 wt %) to highly concentrated regime (7.5 wt %). Our result shows that the PS particle-surface interactions mediated by the soft microgels are greatly affected by the particle concentration, the configuration of those microgels adsorbed on the surfaces, and the structure and packing of microgels in bulk solution. With increasing the microgel concentration (Cmicrogel), the interaction between the PS particle and surface turned from bridging attraction to steric repulsion, and then depletion attraction, which were mainly governed by the adsorption amount and configuration of microgels on the two surfaces. By further increasing Cmicrogel to condensed situation, structural force with oscillated energy wells was detected. The variation of interactions induced by the soft microgels was further confirmed by optical imaging. Crystallization of the PS microparticles appeared at moderate Cmicrogel; however, crystallization was hindered at higher Cmicrogel where the microgels are highly packed in the bulk solution. Furthermore, using TIRM, microgel packing with local energy well (0.1-1.0 kBT) at the highly condensed state (7.5 wt %) was resolved from the interaction profiles. Therefore, the shear force and modulus generated by such microgel packing can be determined as ∼0.2 pN and tens of mPa, respectively, which are much weaker than data given by conventional active methods.