Effect of cross-linking density on the rheological behavior of ultra-soft chitosan microgels at the oil–water interface

In this paper, microgels with uniform particle size were prepared by physically cross-linking the hydrophobically modified chitosan ( h -CS) with sodium phytate (SP). The effects of cross-linking density on the interfacial adsorption kinetics, viscoelasticity, stress relaxation, and micorheological properties of the hydrophobically modified chitosan microgels ( h -CSMs) at the oil–water interface were extensively investigated by the dilatational rheology, compressional rheology, and particle tracing microrheology. The results were correlated with the particle size, morphology, and elasticity of the microgels characterized by dynamic light scattering and atomic force microscopy. It was found that with the increase of cross-linking density, the h -CSMs changed from a polymer-like state to ultra-soft fussy spheres with higher elastic modulus. The compression isotherms demonstrated multi-stage increase caused by the interaction between the shells and that between the cores of the microgels successively. As the increase of cross-linking density, the h -CSMs diffused slower to the oil–water interface, but demonstrating faster permeation adsorption and rearrangement at the oil–water interface, finally forming interfacial layers of higher viscoelastic modulus due to the core-core interaction. Both the initial tension relaxation and the microgel rearrangement after interface expansion became faster as the microgel elasticity increased. The interfacial microrheology demonstrated dynamic caging effect caused by neighboring microgels. This article provides a more comprehensive understanding of the behaviors of polysaccharide microgels at the oil-water interface.