Inorganic/organic hybrid microcapsules: melamine formaldehyde-coated Laponite-based Pickering emulsions

A facile synthesis route to novel inorganic/organic hybrid microcapsules is reported. Laponite nanoparticles are surface-modified via electrostatic adsorption of Magnafloc, an amine-based polyelectrolyte allowing the formation of stable oil-in-water Pickering emulsions. Hybrid microcapsules can be subsequently prepared by coating these Pickering emulsion precursors with dense melamine formaldehyde (MF) shells. Employing a water-soluble polymeric stabiliser, poly(acrylamide-co-sodium acrylate) leads to stable hybrid microcapsules that survive an alcohol challenge and the ultrahigh vacuum conditions required for SEM studies. Unfortunately, the presence of this copolymer also leads to secondary nucleation of excess MF latex particles in the aqueous continuous phase. However, since the Magnafloc is utilised at submonolayer coverage when coating the Laponite particles, the nascent cationic MF nanoparticles can deposit onto anionic surface sites on the Laponite, which removes the requirement for the poly(acrylamide-co-sodium acrylate) component. Following this electrostatic adsorption, the secondary amine groups on the Magnafloc chains can react with the MF, leading to highly robust cross-linked MF shells. The absence of the copolymer leads to minimal secondary nucleation of MF latex particles, ensuring more efficient deposition at the surface of the emulsion droplets. However, the MF shells appear to become more brittle, as SEM studies reveal cracking on addition of ethanol.