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We have studied the complete two-dimensional phase diagram of a core-shell microgel-laden fluid interface by synchronizing its compression with the deposition of the interfacial monolayer. Applying a new protocol, different positions on the substrate correspond to different values of the monolayer surface pressure and specific area. Analyzing the microstructure of the deposited monolayers, we discovered an isostructural solid-solid phase transition between two crystalline phases with the same hexagonal symmetry, but with two different lattice constants. The two phases corresponded to shell-shell and core-core inter-particle contacts, respectively; with increasing surface pressure the former mechanically failed enabling the particle cores to come into contact. In the phase-transition region, clusters of particles in core-core contacts nucleate, melting the surrounding shell-shell crystal, until the whole monolayer moves into the second phase. We furthermore measured the interfacial rheology of the monolayers as a function of the surface pressure using an interfacial microdisk rheometer. The interfaces always showed a strong elastic response, with a dip in the shear elastic modulus in correspondence with the melting of the shell-shell phase, followed by a steep increase upon the formation of a percolating network of the core-core contacts. These results demonstrate that the core-shell nature of the particles leads to a rich mechanical and structural behavior that can be externally tuned by compressing the interface, indicating new routes for applications, e.g. in surface patterning or emulsion stabilization.

Monolayers of micro- and nanoparticles at fluid interfaces are a key component in a variety of applications, ranging from particle lithography to stabilizers in foams or emulsions. In addition to commonly used "hard" colloids, soft polymeric particles like microgels are attracting increasing attention due to their potential in the fabrication of tailored and responsive assemblies. In particular, regular hexagonal arrays of microgels have been previously deposited after assembly at a fluid interface. While the arrangement cannot be easily controlled after adsorption and self-assembly from the bulk phase, specific structures can be achieved by compressing an interfacial microgel monolayer spread in a Langmuir trough and by transferring it onto substrates at distinct compression states. The degree of ordering after compression surpasses the one that is reached after self-assembly from the bulk and is, in general, independent from the presence of charges and different microgel morphologies. As a consequence, by monitoring the surface pressure during compression it is possible to produce highly ordered microgel arrays where the interparticle distance can be systematically and externally controlled.

The aim of this paper is to determine how microgels adsorb at a model oil-water interface and how they adapt their conformation to compression, which gives rise to surface elasticity depending on the microgel packing. The structure of the film is determined by the Langmuir films approach (forced compression) and compared to spontaneous adsorption using the pendant drop method. The behaviour of microgels differs significantly from that of non-deformable particles but resembles that of linear polymers or proteins. We also correlate the properties of microgels spontaneously adsorbed at model interfaces to their forced adsorption during emulsification. Finally we propose a route to easily control a posteriori the microgel packing at the surface of droplets and the flow properties of emulsions stabilised by the microgels.