ABSTRACT
Temperature-sensitive rod-like colloidal particles were synthesized by grafting a temperature-responsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMA), on the surface of high aspect ratio silica rods by surface-initiated atom transfer radical polymerization. The stability of the grafted polymer on the surface of the particles in aqueous solutions was found to deteriorate with time, leading to a gradual decrease of the polymer content of the hybrid colloids, which was attributed to the mechanically activated hydrolysis of the labile bonds at the polymer-silica interface. The polymer degrafting was significantly suppressed by first growing a hydrophobic poly(methyl methacrylate) block onto the particle surface to act as a barrier layer for the penetration of water molecules at the polymer-particle interface, followed by chain-extension with the hydrophilic PDMA chains. Dynamic light scattering, microscopy, and rheological measurements revealed that the PDMA block conferred a temperature-responsive behavior to the rod-like particles, which formed aggregates at temperatures above the lower critical solution temperature (LCST) of the polymer. However, in contrast to their spherical counterparts, the polymer-grafted rod-like particles did not exhibit complete thermo-reversibility upon lowering the solution temperature below the LCST of PDMA, which was reflected by different values of the diffusion coefficient for the heating and cooling cycles, indicating an irreversible rod particle aggregation upon increasing the temperature.
ABSTRACT
A combination of rheology, optical microscopy and computer simulations was used to investigate the microstructural changes of a semi-dilute suspension of attractive rigid rods in an imposed shear flow. The aim is to understand the relation of the microstructure with the viscoelastic response, and the yielding and flow behaviour in different shear regimes of gels built from rodlike colloids. A semi-dilute suspension of micron sized, rodlike silica particles suspended in 11 M CsCl salt solution was used as a model system for attractive rods' gel. Upon application of steady shear the gel microstructure rearranges in different states and exhibits flow instabilities depending on shear rate, attraction strength, volume fraction and geometrical confinement. At low rod volume fractions, the suspension forms large, vorticity aligned, particle rich flocs that roll in the flow-vorticity plane, an effect that is due to an interplay between hydrodynamic interactions and geometrical confinement as suggested by computer simulations. Experimental data allow the creation of a state diagram, as a function of volume fraction and shear rates, identifying regimes of stable (or unstable) floc formation and of homogeneous gel or broken clusters. The transition is related to dimensionless Mason number, defined as the ratio of shear forces to interparticle attractive force.
ABSTRACT
Polymer microrods of aspect ratio â¼10, and tunable flexibility are attractive model systems to study density and index matched liquid crystalline phases. However, the synthesis of anisotropic polymer particles is arduous, due to the lack of directional polymer growth mechanisms. In this work, non-cross-linked, hollow polymer microrods are developed from a dense block copolymer brush grown from the surface of micron-sized silica rods. The copolymer brush, comprising a hydrophobic inner block and a hydrophilic outer layer, is synthesized by surface-initiated atom transfer radical polymerization, and is exploited in the preparation of robust polymer rod particles in water, following etching of the inorganic core. The solvent-incompatible inner block is crucial for the synthesis of the rod-like polymer particles, in the absence of chemical cross-links, and the block copolymer composition affects the colloidal stability and flexibility of the hollow anisotropic colloids. For shorter hydrophobic block lengths, well-defined, yet flexible, hollow rods are obtained, whereas increasing the hydrophobic content of the copolymer results in rigid, tube-like particles. The approach is generic and could be easily employed to obtain polymer rod particles in any solvent medium, upon the appropriate selection of the solvent-incompatible inner block and the solvent-compatible outer block.
