Shape control of nanostructured cone-shaped particles by tuning the blend morphology of A-b-B diblock copolymers and C-type copolymers within emulsion droplets
Block copolymers (BCPs) under colloidal confinement can provide an effective route to produce non-spherical particles. However, the resulting structures are typically limited to spheroids, and it remains challenging to achieve a higher level of control in the particle shape with different symmetries. Herein, we exploit the blend of BCPs and statistical copolymers (sCPs) within emulsion droplets to develop a series of particles with different symmetries (i.e. Janus-sphere and cone-shaped particles). The particle shape is tunable by controlling the phase behavior of the polymer blend consisting of a poly(styrene-block-1,4-butadiene) (PS-b-PB) BCP and a poly(methylmethacrylate-statistical-(4-acryloylbenzophenone)) (P(MMA-stat-4ABP)) sCP. A key strategy for controlling the phase separation of the polymer blend is to systematically tune the incompatibility between the BCP and sCP by varying the composition of the sCPs (ϕ4ABP, mole fraction of 4ABP). As a result, a sequential morphological transition from a prolate ellipsoid, to a Janus-sphere, to a cone-shaped particle is observed with the increase of ϕ4ABP. We further demonstrate that the shape-anisotropy of cone-shaped particles can be tailored by controlling the particle size and the Janusity, which is supported by quantitative calculation of the particle shape-anisotropy from the theoretical model. Also, the importance of the shape control of the cone-shaped particles with high uniformity in a batch is demonstrated by investigating their coating properties, in which the deposited coating pattern is a strong function of the shape-anisotropy of the particles.