Langmuir, Vol.26, No.2, 716-723, 2010
Controlled Self-Assembly of Quantum Dot-Block Copolymer Colloids in Multiphase Microfluidic Reactors
The controlled self-assembly of large compound quantum dot micelles (QDCMs), consisting of constituents of polymer-stabilized quantum dots (QDs) and amhiphilic polystyrene-b-poly(acrylic acid) stabilizing chains, in gas-liquid segmented microfluidic reactors is demonstrated, Self-assembly is initiated by fast mixing of water with the polymer constituents via chaotic advection, as liquid plugs containing reactants move through a sinusoidal mixing channel. The resulting QDCMs are then processed within a postformation channel, where circulating flow patterns develop within the liquid plugs, followed by off-chip quenching and analysis by transmission electron microscopy (TEM). Particle processing via circulating now is found to involve a combination of particle growth via collision-induced coalescence and shear-induced particle breakup. The final mean QDCM sizes represent kinetic states arising from the competition between these two mechanisms, depending on tunable chemical and flow parameters. A systematic investigation of the experimental variables that influence particle size and polydispersity, including water concentration, now rate, and the gas-to-liquid now ratio, is conducted, demonstrating tunability of QDCM sizes in the range of similar to 40-140 nm. The importance of shear-induced particle breakup in the limit of high shear is illustrated by a common minimum particle size, 41 +/- 1 nm, which is achieved for all water contents by increasing the total flow rate to sufficiently high values.