The use of the Janus motif in colloidal particles, i.e., anisotropic surface properties on opposite faces, has gained significant attention in the bottom-up assembly of novel functional structures, design of active nanomotors, biological sensing and imaging, and polymer blend compatibilization. This review is focused on the behavior of Janus particles in interfacial systems, such as particle-stabilized (i.e., Pickering) emulsions and foams, where stabilization is achieved through the binding of particles to fluid interfaces. In many such applications, the interface could be subjected to deformations, producing compression and shear stresses. Besides the physicochemical properties of the particle, their behavior under flow will also impact the performance of the resulting system. This review article provides a synopsis of interfacial stability and rheology in particle-laden interfaces to highlight the role of the Janus motif, and how particle anisotropy affects interfacial mechanics.
The presence of contamination in sodium dodecyl sulfate (SDS) solutions in the form of dodecanol (LOH) is known to drastically affect the resulting interfacial properties such as surface tension (SFT) and rheology. Dodecanol molecules, which are the product of SDS hydrolysis and are inherently present in SDS solutions, have higher surface activity compared to SDS because they are less soluble in water. A characteristic dip in the SFT isotherm is an indicator of the dodecanol contamination in the sample. The presence of an electrolyte in the solution impacts the surface activity of SDS and its critical micelle concentration, and could yield SFT isotherms that closely match those obtained for pure SDS samples. The interpretation of the isotherms in such cases could thus lead to misinterpretation of the surface purity. In this work, we have examined the SFT isotherms for SDS solutions in both the absence and presence of electrolyte. We have fitted the isotherms to three different thermodynamic adsorption models to estimate the amount of dodecanol present in the sample. We have applied the estimated values for the LOH content in a two-component rheological model to predict the viscoelasticity of such surfactant-laden surfaces. We have compared these results with the experimentally measured interfacial rheological properties. Our findings demonstrate that the presence of impurities can be captured under dynamic expansion and contractions, even for solutions containing background electrolyte.
Interfacial rheology studies were conducted to establish a connection between the rheological characteristics of particle-laden interfaces and the stability of Pickering foams. The behavior of foams stabilized with fumed and spherical colloidal silica particles was investigated, focusing on foam properties such as bubble microstructure and liquid content. Compared to a sodium dodecyl sulfate-stabilized foam, Pickering foams exhibited a notable reduction in bubble coarsening. Drop shape tensiometry measurements on particle-coated interfaces indicated that the Gibbs stability criterion was satisfied for both particle types at various surface coverages, supporting the observed arrested bubble coarsening in particle-stabilized foams. However, although the overall foam height was similar for both particle types, foams stabilized with fumed silica particles demonstrated a higher resistance to liquid drainage. This difference was attributed to the higher yield strain of interfacial networks formed by fumed silica particles, as compared to those formed by spherical colloidal particles at similar surface pressures. Our findings highlight that while both particles can generate long-lasting foams, the resulting Pickering foams may exhibit variations in microstructure, liquid content, and resistance to destabilization mechanisms, stemming from the respective interfacial rheological properties in each case.
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