Kinetics of the glass transition of fragile soft colloidal suspensions

Abstract

Microscopic relaxation timescales are estimated from the autocorrelation functions obtained by dynamic light scattering experiments for Laponite suspensions with different concentrations ($C_{L}$), added salt concentrations ($C_{S}$) and temperatures ($T$). It has been shown in an earlier work [Soft Matter, 10, 3292-3300 (2014)] that the evolutions of relaxation timescales of colloidal glasses can be compared with molecular glass formers by mapping the waiting time ($t_{w}$) of the former with the inverse of thermodynamic temperature ($1/T$) of the latter. In this work, the fragility parameter $D$, which signifies the deviation from Arrhenius behavior, is obtained from fits to the time evolutions of the structural relaxation timescales. For the Laponite suspensions studied in this work, $D$ is seen to be independent of $C_{L}$ and $C_{S}$, but is weakly dependent on $T$. Interestingly, the behavior of $D$ corroborates the behavior of fragility in molecular glass formers with respect to equivalent variables. Furthermore, the stretching exponent $\beta$, which quantifies the width $w$ of the spectrum of structural relaxation timescales is seen to depend on $t_{w}$. A hypothetical Kauzmann time $t_{k}$, analogous to the Kauzmann temperature for molecular glasses, is defined as the timescale at which $w$ diverges. Corresponding to the Vogel temperature defined for molecular glasses, a hypothetical Vogel time $t^{\infty}_{\alpha}$ is also defined as the time at which the structural relaxation time diverges. Interestingly, a correlation is observed between $t_{k}$ and $t^{\infty}_{\alpha}$, which is remarkably similar to that known for fragile molecular glass formers. A coupling model that accounts for the $t_{w}$-dependence of the stretching exponent is used to analyse and explain the observed correlation between $t_{k}$ and $t^{\infty}_{\alpha}$.