title: Surfactant-enhanced cellulose nanocrystal Pickering emulsions.
abstract: The effect of surfactants on the properties of Pickering emulsions stabilized by cellulose nanocrystals (CNCs) was investigated. Electrophoretic mobility, interfacial tension, confocal microscopy and three-phase contact angle measurements were used to elucidate the interactions between anionic CNCs and cationic alkyl ammonium surfactants didecyldimethylammonium bromide (DMAB) and cetyltrimethylammonium bromide (CTAB). Both surfactants were found to adsorb onto CNCs with concentration-dependent morphology. At low concentrations, individual surfactant molecules adsorbed with alkyl tails pointing outward leading to hydrophobic CNCs. At higher concentrations, above the surfactant's apparent critical micelle concentration, surfactant aggregate morphologies on CNCs were inferred and the hydrophobicity of CNCs decreased. DMAB, which has two alkyl tails, rendered the CNCs more hydrophobic than CTAB which has only a single alkyl tail, at all surfactant concentrations. The change in CNC wettability from surfactant adsorption was directly linked to emulsion properties; adding surfactant increased the emulsion stability, decreased the droplet size, and controlled the internal phase of CNC Pickering emulsions. More specifically, a double transitional phase inversion, from oil-in-water to water-in-oil and back to oil-in-water, was observed for emulsions with CNCs and increasing amounts of DMAB (the more hydrophobic surfactant). With CNCs and CTAB, no phase inversion was induced. This work represents the first report of CNC Pickering emulsions with surfactants as well as the first CNC Pickering emulsions that can be phase inverted. The ability to surface modify CNCs in situ and tailor emulsions by adding surfactants may extend the potential of CNCs to new liquid formulations and extruded/spray-dried materials.
authors.affiliation: Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L7, Canada. Electronic address: huz7@mcmaster.ca.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Hu
authors.affiliation: Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L7, Canada. Electronic address: ballinse@mcmaster.ca.
authors.forename: Sarah
authors.initials: S
authors.lastname: Ballinger
authors.affiliation: Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L7, Canada. Electronic address: peltonrh@mcmaster.ca.
authors.forename: Robert
authors.initials: R
authors.lastname: Pelton
authors.affiliation: Department of Chemical Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4L7, Canada. Electronic address: ecranst@mcmaster.ca.
authors.forename: Emily D
authors.initials: ED
authors.lastname: Cranston
mesh_terms: D000388:Air; D002482:Cellulose / Q000737:chemistry*; D004355:Drug Stability; D004655:Emulsions / Q000737:chemistry*; D018613:Microscopy, Confocal; D053758:Nanoparticles / Q000737:chemistry*; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D004655:Emulsions; D013501:Surface-Active Agents; D014867:Water; D002482:Cellulose
keywords: Cellulose nanocrystals; Confocal microscopy; Double phase inversion; Emulsions; Fluorescent labeling; Pickering; Surface and interfacial tension; Surfactants