Thermoresponsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with Alkyl Polyoxyethylene Ether Nonionic Surfactant.

We put forward a simple protocol to prepare thermoresponsive Pickering emulsions. Using hydrophilic silica nanoparticles in combination with a low concentration of alkyl polyoxyethylene monododecyl ether (C12En) nonionic surfactant as emulsifier, oil-in-water (o/w) emulsions can be obtained, which are stable at room temperature but demulsified at elevated temperature. The stabilization can be restored once the separated mixture is cooled and rehomogenized, and this stabilization-destabilization behavior can be cycled many times. It is found that the adsorption of nonionic surfactant at the silica nanoparticle-water interface via hydrogen bonding between the oxygen atoms in the polyoxyethylene headgroup and the SiOH groups on particle surfaces at low temperature is responsible for the in situ hydrophobization of the particles rendering them surface-active. Dehydrophobization can be achieved at elevated temperature due to weakening or loss of this hydrogen bonding. The time required for demulsification decreases with increasing temperature, and the temperature interval between stabilization and destabilization of the emulsions is affected by the surfactant headgroup length. Experimental evidence including microscopy, adsorption isotherms, and three-phase contact angles is provided to support the mechanism.