Direct Observation of the Formation of Liquid Protrusions on Polymer Colloids and their Coalescence

Monodisperse nonspherical poly (methyl methacrylate) (PMMA) particles where a central core particle had grown two extra “lobes”, or protrusions, placed opposite each other were successfully synthesized by swelling and subsequent polymerization of cross-linked PMMA spheres with methyl methacrylate and the cross-linker ethylene glycol dimethacrylate. The use of large (3 μm) seed particles allowed for real-time monitoring of the swelling and deswelling of the cross-linked particles with optical microscopy. First, a large number of small droplets of swelling monomers formed simultaneously on the surface of the seed particles, and then fused together until under certain conditions two protrusions remained on opposite sides of the seed particles. The yield of such particles could be made up to 90% with a polydispersity of 7.0%. Stirring accelerated the transfer of the swelling monomers to the seed particles. Stirring was also found to induce self-assembly of the swollen seed particles into a wide variety of n-mers, consisting of a certain number, n, of swollen seed particles. The formation of these structures is guided by the minimization of the interfacial free energy between the seed particles, liquid protrusions and aqueous phase, but stirring time and geometrical factors influence it as well. By inducing polymerization the structures could be made permanent. Some control over the topology as well as overall size of the clusters was achieved by varying the stirring time before polymerization. 3D models of possible particle structures were used to identify all projections of the structures obtained by scanning electron microscopy. These models also revealed that the seed particles inside the central coalesced body were slightly compressed after polymerization. By extending the synthesis of the monodisperse particles with n = 1 to (slightly) different monomers and/or different cores, an important class of patchy particles could be realized.