Deformability and Solvent Penetration in Soft Nanoparticles at Liquid-Liquid Interfaces

TL;DR

This study uses large-scale simulations to explore how soft nanogels deform and allow solvent penetration at liquid-liquid interfaces, revealing how their internal architecture and interfacial strength influence permeability and miscibility.

Contribution

It provides new insights into the effects of nanogel architecture and interfacial strength on deformability, permeability, and miscibility at liquid-liquid interfaces, considering explicit solvent interactions.

Findings

Regular networks have higher liquid uptake than disordered ones.

Uptake and invasion are optimized at 15-20% cross-linking degree.

Miscibility inside nanogels can be enhanced up to five times with increased interfacial strength.

Abstract

Soft nanoparticles hold promise as smart emulsifiers due to their high degree of deformability, permeability and stimuli responsive properties. By means of large-scale simulations we investigate the structural properties of nanogels at liquid-liquid (A-B) interfaces and the miscibility of the liquids inside the nanogels, covering the whole range of interfacial strength from the limit of single-liquid to the case of stiff interfaces. To study the role of the internal architecture and deformability of the nanogel we simulate a realistic disordered and an ideal regular network, for a broad range of cross-linking degrees. Unlike in previous investigations on liquid miscibility, excluded volume interactions are considered for both the monomers and the explicit solvent particles. The nanogel permeability is analysed by using an unbiased grid representation that accounts for the surface fluctuations and adds to the density profiles the exact number of liquid particles inside the nanogel. The better packing efficiency of the regular network leads to higher values of the total liquid uptake and the invasive capacity (A-particles in B-side and viceversa than in the disordered network, though differences vanish in the limit of rigid interfaces. Uptake and invasion are optimized at a cross-linking degree that depends on the interfacial strength, tending to 15 - 20% for moderate and stiff interfaces. As the interfacial strength increases, the miscibility inside the nanogel is enhanced by a factor of up to 5 with respect to the bare interface, with the disordered networks providing a better mixing than their ideal counterparts. The emerging scenario reported here provides general guidelines for tuning the shape, uptake, invasive, and mixing capacities of nanogels adsorbed at liquid-liquid interfaces.