Crowded solutions of multiarm star polymers, representing model colloidal spheres with ultrasoft repulsive interactions, undergo a reversible gelation transition upon heating in solvents of intermediate quality (between good and $\Theta ).\mathrm{}$ This unusual phenomenon is due to the kinetic arrest of the swollen interpenetrating spheres at high temperatures, forming clusters, in analogy to the colloidal glass transition. In this work we demonstrate that the choice of the solvent has a dramatic effect on the gelation transition, because of the different degree of star swelling (at the same temperature) associated with the solvent quality. We construct a generic kinetic phase diagram for the gelation of different stars in different solvents (gelation temperature against effective volume fraction, $\phi )$ and propose a critical “soft sphere close packing” volume fraction ${\phi }_c$ distinguishing the temperature-induced (for $\phi <{\phi }_c)$ from the concentration-induced (for $\phi >{\phi }_c)$ glass-like gelation. We conclude that appropriate selection of the solvent allows for manipulation of the sol-gel transition in such ultrasoft colloids.

• Received 23 July 2002

DOI:https://doi.org/10.1103/PhysRevE.66.051804