Compression, expansion and relaxation of soft colloidal monolayers at the air/water interface

Abstract

The phase behavior of soft and deformable microgels at fluid interfaces is typically studied with a Langmuir trough and using uniaxial compression. In situ investigations that shine light on the structural arrangements and changes during compression are scarce. Knowledge on the phase behavior is mostly generated from ex situ observations after transfer of monolayers from the fluid interface onto a substrate. Similarly, little is known about the impact of the compression geometry and potentially occurring relaxation processes after compression. Here, we use small-angle light scattering implemented in a Langmuir trough to follow the evolution of microgel monolayers in situ and in real time. We use core–shell microgels as soft model colloids where the rigid cores ensure large contrast for light diffraction. Not only the influence of compression but also the influence of expansion is studied as well as relaxation after previous compression/expansion. At sufficiently high surface pressures, densely packed monolayers of partially compressed microgels are obtained at air/water interfaces. In this regime, the monolayer response upon manipulation of the accessible interfacial area is reversible over many cycles. The uniaxial geometry of this manipulation leads to anisotropic deformation of the monolayer seen by the recorded structure factor. Upon stopping compression/expansion, anisotropy relaxes with two time constants but full isotropy is not recovered. This work underlines the potential and necessity of in situ ensemble techniques for investigating soft colloidal monolayers at fluid interfaces. With our results, we advance the understanding of how soft colloids react to uniaxial compression/expansion.