The effect of free polymer on the interactions and the glass transition dynamics of microgel colloids

By studying the phase behaviour and the short range order of polystyrene microgel colloids in a good solvent we demonstrated that these particles can be considered as hard spheres or nearly hard spheres if the internal cross link density is made sufficiently high. A binary mixture of 1:50 crosslinked (1 crosslink per 50 monomers) particles with a size ratio R(small)/R(large) = 0.83 and a number ratio N(small)/N(large) = 2.7 was characterized with respect to the short range order and glass transition dynamics. We found that this mixture can be mapped onto a one-component hard sphere system with an effective polydispersity of 11%, even though for the particle interactions an inverse power potential u(r) alpha r(-35) was established. The only significant difference observed was a shift of the glass transition to a higher volume fraction of 0.595. Thus, the binary mixture was used as a non-crystallizing reference system to study the effect of free polymer on interactions and glass transition dynamics. Addition of linear polystyrene with a size ratio delta = R(g,polymer)/R(colloid) = 0.054 induced short-ranged depletion attractions between microgel particles. In the case of a glassy sample already a rather small amount of polymer leads to melting of the glass and a re-entrant glass transition is observed at high polymer content. From the difference of the line shapes of the density autocorrelation functions on approaching the different transition lines. measured over the full dynamic range, a change of the freezing mechanism from a packing-driven glass transition at low polymer content to a bonding-driven glass transition at high polymer content was deduced.