Pickering Emulsions Synergistically Stabilized by Aliphatic Primary Amines and Silica Nanoparticles

Innovation in emulsion compositions is necessary to enrich emulsion formulations and applications. Herein, Pickering emulsions were prepared using silica nanoparticles and aliphatic primary amines with an oil-water ratio of 1:1 (v/v). Contact angle experiments revealed that the in situ hydrophobization of nanoparticles was caused by the surface adsorption of amine molecules. Notably, the interactions between amine compounds and the surface of silica nanoparticles were electrostatic attractions and mutual hydrogen bonding. The existence of hydrogen bonds was further confirmed by demulsification experiments using a chaotropic agent DMF and increasing temperatures. The hydrophobicity of silica nanoparticles can be effectively improved using most commercially available aliphatic primary amines such as n-hexylamine, n-octylamine, n-decylamine, dodecylamine, and tetradecylamine. The minimum concentrations of the aforementioned amines necessary for stabilizing the emulsions with 0.3 wt % silica nanoparticles are 3, 0.6, 0.3, 0.06, and 0.03 mM, respectively, decreasing significantly with increasing alkyl chain length. With the increase of the amine concentrations, the hydrophobicity of silica particles monotonically increased and finally resulted in the inversion of emulsions. The amine concentrations for emulsion phase inversion were 150, 40, 30, 20, and 20 mM, respectively, in the presence of 0.3 wt % silica nanoparticles. In this work, silica nanoparticles were hydrophobized using aliphatic primary amines. The composite stabilizers developed are useful for developing novel stimuli-responsive Pickering emulsions, while the synergistic effects introduced herein are also helpful in expanding the hydrophobization methods available for nanoparticles.