Interplay between Caging and Bonding in Binary Concentrated Colloidal Suspensions.

Abstract

When a liquid becomes dynamically arrested, a gel, a repulsive glass, or an attractive glass state will form. Bonding and caging mechanisms decide their static structures and dynamic properties. To better understand their interplay, the competition between bonding and caging in a binary mixture of polystyrene core/poly( N-isopropylacrylamide) shell (CS) microgels and sulfonated polystyrene (PSS) particles is studied. CS microgels have short-range attraction above the volume phase transition temperature, whereas PSS species experiences relatively long-range electrostatic repulsion. Adding more PSS into the binary mixture will, of course, increase the total effective volume fraction but lead to different properties in gel or glass states. For instance, in gels, it increases the localization length and weakens the gel, whereas in glass, it decreases the localization length and strengthens the glass. This thus implies that the static and dynamic properties of gels are mainly controlled by bonding and those of both repulsive and attractive glasses are governed by caging. On the other hand, increasing the temperature will decrease the effective volume fraction because of the volume phase transition of the CS microgels. A discontinuous repulsive glass-to-liquid-to-gel transition can be observed when the PSS concentration is low, but a continuous repulsive glass-to-gel transition can also be observed with the increase of the PSS concentration. This may hint that glass transition and physical gelation share a similar mechanism, whereas the former has a longer relaxation time.