Compression and Ordering of Microgels in Monolayers Formed at Liquid-Liquid Interfaces: Computer Simulation Studies.

Monolayers of polymer microgels adsorbed at the liquid interfaces were studied by dissipative particle dynamics simulations. The results demonstrated that the compressibility of the monolayers can be widely tuned by varying the cross-linking density of the microgels and their (in)compatibility with the immiscible liquids. In particular, the compression of the monolayers (increase of 2D concentration of the microgels) leads to the decrease of their lateral size. Herewith, the shape of the individual soft particles gradually changes from oblate (diluted 2D system) to nearly spherical (compressed monolayer). The polymer concentration profiles plotted along the normal to the interface reveal a nonmonotonous shape with a sharp maximum at the interface. This is a consequence of the shielding effect: saturation of the interface by monomer units of the subchains is driven by minimization of unfavorable contacts between the immiscible liquids and is opposed by elasticity of the network. The decrease of the interfacial tension upon concentration (compression) of the monolayer is quantified. It has been demonstrated that the interfacial tension significantly differs if the solubility of the polymer chains of the microgel network in the liquids changes. These results correlate well with experimental data. The examination of the microgels' crystalline ordering in monolayers demonstrated a nonmonotonous dependency on the compression degree (microgel concentration). Finally, the worsening of the solvent quality leads to the collapse of the microgels in monolayer and nonmonotonous behavior of the interfacial tension.