The
understanding of the shell formation mechanism for the novel
encapsulation technique via integrating microfluidic T-junction and
interfacial polymerization is not only important to fabricate high-quality
polyamine microcapsules but also of practical and theoretical significance
to the wide application of this method based on nonequilibrium droplets.
Herein, using pure polyamine as a targeting core, the shell formation
mechanism was investigated by studying the achieved shell structures
of the preliminary and final microcapsules and the behavior of nonequilibrium
polyamine droplets in the coflow solvent. It reveals the shell has
a multilayered structure, i.e., a rough outer layer, a porous middle
layer, and a thin but dense inner layer, and the porous middle layer
consists of pores with two size levels. This shell structure was correlated
to fractal geometry of the polyamine droplet before being encapsulated,
which was generated attributed to the interactions between the nonequilibrium
polyamine droplet and the coflow solvent, i.e., interdiffusion and
spontaneous emulsification. To achieve robust microcapsules, shell
thickness and tightness were also studied by varying the composition
of the reaction solution in terms of diisocyanate concentration and
type of solvent with different polarity. The effect of these two key
parameters on shell in this method is very similar to that in the
traditional interfacial polymerization. In addition, the influence
of the shell-forming stage and shell-growth stage on the robustness
of microcapsule was discussed, indicating the former is decisive.