Hetero-assembly of colloidal particles in concentrated non-aqueous suspensions by polymer dispersant design

Although many colloidal assembling systems have been reported, most systems suffer from severe aggregation under high solid concentrations, which can often be observed in typical hetero-aggregation system. In this study, we created a hetero-assembly system using concentrated (~50 vol%) suspensions by mixing large SiO₂ particles modified with polyacrylic acid partially complexed with oleylamine (PAA-OAm) and small SiO₂ particles modified with polyethyleneimine partially complexed with oleic acid (PEI-OA) in a non-aqueous solvent. We demonstrated that hetero-assembly is driven by the interactions between the uncomplexed carboxyl/amine groups of the PAA/PEI present on the particles, while severe aggregation is simultaneously prevented by the steric repulsions of the aliphatic oleyl chains. Comparison of the cross sections of the in-situ solidified hetero-assembled suspensions with those of ideally assembled structures which were reproduced by a simulation considering the statistical distribution of particles strongly supported successful particle assembling via the proposed approach. The results revealed that the OA content in the PEI-OA complex was the dominant factor that controlled the dispersion and assembling state of the binary particles. The significance of this study is that our findings will provide a class of colloidal dispersion state which binary particles were assembled in a high solid content suspension without forming strong aggregates.