Hydrophobically modified chitosan biopolymer connects halloysite nanotubes at the oil-water interface as complementary pair for stabilizing oil droplets

The integration of cationic and hydrophobic functionalities into hydrophobically modified chitosan (HMC) biopolymer facilitates complementary emulsion stabilization with negatively charged halloysite clay nanotubes (HNT). Oil-in-water emulsions with smaller droplet sizes and significantly improved interfacial resistance to droplet coalescence are obtained on complementary emulsion stabilization by HNT and HMC compared to the individual emulsifiers alone. Contact angle measurements shows that the adsorption of the cationic HMC onto the negatively charged HNT modifies the surface wettability of the nanotubes, facilitating the attachment of the nanotubes to the oil-water interface. High resolution cryo-SEM imaging reveals that free HMC chains locks the nanotubes together at the oil-water interface, creating a high barrier to droplet coalescence. The emulsion stability is an order of magnitude higher for conditions in which the aqueous HNT dispersion is stabilized by the HMC compared to conditions where the negatively charged HNT is strongly flocculated by the cationic HMC. The hydrophobic interaction between HMC chains, insertion of HMC hydrophobes into the oil phase and electrostatic interactions between HMC and HNT are proposed as key mechanisms driving the increased emulsion stability. For potential application as a dispersant system for crude oil spill treatment, the nanotubular morphology of HNT was further exploited for the encapsulation of the water-insoluble surfactant, sorbitan monooleate (Span 80). The HMC and HNT sterically strengthens the oil-water interfacial layer while release of the Span 80 surfactant from the HNT lumen lowers the oil-water interfacial tension. The concepts advanced here are relevant in the development of environmentally-benign dispersants for oil spill remediation.