ABSTRACT
Asphaltenes are surface-active molecules that exist naturally in crude oil. They adsorb at the water-oil interface and form viscoelastic interfacial films that stabilize emulsion droplets, making water-oil separation extremely challenging. There is, thus, a need for chemical demulsifiers to disrupt the interfacial asphaltene films, and, thereby, facilitate water-oil separation. Here, we examine ethylcellulose (EC) as a model demulsifier and measure its impact on the interfacial properties of asphaltene films using interfacial shear microrheology. When EC is mixed with an oil and asphaltene solution, it retards the interfacial stiffening that occurs between the oil phase in contact with a water phase. Moreover, EC introduces relatively weak regions within the film. When EC is introduced to a pre-existing asphaltene film, the stiffness of the films decreases abruptly and significantly. Direct visualization of interfacial dynamics further reveals that EC acts inhomogeneously, and that relatively soft regions in the initial film are seen to expand. This mechanism likely impacts emulsion destabilization and provides new insight to the process of demulsification.
ABSTRACT
Surface-active asphaltene molecules are naturally found in crude oil, causing serious problems in the petroleum industry by stabilizing emulsion drops, thus hindering the separation of water and oil. Asphaltenes can adsorb at water-oil interfaces to form viscoelastic interfacial films that retard or prevent coalescence. Here, we measure the evolving interfacial shear rheology of water-oil interfaces as asphaltenes adsorb. Generally, interfaces stiffen with time, and the response crosses over from viscous-dominated to elastic-dominated. However, significant variations in the stiffness evolution are observed in putatively identical experiments. Direct visualization of the interfacial strain field reveals significant heterogeneities within each evolving film, which appear to be an inherent feature of the asphaltene interfaces. Our results reveal the adsorption process and aged interfacial structure to be more complex than that previously described. The complexities likely impact the coalescence of asphaltene-stabilized droplets, and suggest new challenges in destabilizing crude oil emulsions.
ABSTRACT
Efficient encapsulation of tetraethylenepentamine (TEPA), as an example aliphatic amine, was achieved by an emulsion-templated, in situ polymerization. Hydrophobically modified clay nanoplatelets were employed as emulsifiers to obtain water-in-oil (W/O) dispersions followed by interfacial polymerization between a portion of the TEPA cargo and polymethylene polyphenylene isocyanate (PMPPI). The resultant capsules exhibit spherical shape, desirable thermal stability, modest barrier properties, and shear-induced release in an epoxide monomer mixture. Most importantly, a significant gain in capsule barrier properties was realized by introducing poly(allyl amine) (pAAm) as an interface-selective reactive additive in the Pickering emulsions. In addition to the fundamental interest of pAAm localization and interface-selective reactivity, this microencapsulation system for aliphatic amines has technological potential in coating, self-healing, and drug-delivery applications.
