Probing the Internal Heterogeneity of Responsive Microgels Adsorbed to an Interface by a Sharp SFM Tip: Comparing Core-Shell and Hollow Microgels.

Microgels composed of thermoresponsive polymer poly( N-isopropylacrylamide) (PNIPAM) are interfacial active. Their adsorption leads to deformation, causing conformational changes that have profound effects on the macroscopic properties of these films. Yet, methods to quantitatively probe the local density are lacking. We introduced scanning force microscopy (SFM) to quantitatively probe the internal structure of microgels physically adsorbed on a solid (SiO2)/water interface. Using a sharp SFM tip, we investigated the two types of microgels: (i) core-shell microgels featuring a hard silica core and a PNIPAM shell and (ii) hollow microgels obtained by dissolution of the silica core. Thus, both systems have the same polymer network as the peripheral structure but a distinctly different internal structure, that is, a rigid core versus a void. By evaluating the force-distance curves, the force profile during insertion of the tip into the polymer network enables to determine a depth-dependent contact resistance, which closely correlates with the density profiles determined in solution by small-angle neutron scattering. We found that the cavity of the swollen hollow microgels is still present when adsorbed to the solid substrate. Remarkably, while currently used techniques such as colloidal probe or reflectometry only provide an average of the z-profile, the methodology introduced herein actually probes the real three-dimensional density profile, which is ultimately important to understand the macroscopic behavior of microgel films. This will bridge the gap between the colloidal probe experiments that deform the microgel globally and the insertion in which the disturbance is located near the tip.