Diffusion Decoupling in Binary Colloidal Systems Observed with Contrast Variation Multispeckle Diffusing Wave Spectroscopy

[Image: see text] In the study of colloidal glasses, crystallization is often suppressed by leveraging size polydispersity, ranging from systems where particle sizes exhibit a continuous distribution to systems composed of particles of two or more distinct sizes. The effects of the disparities in size of the particles on the colloidal glass transition are not yet completely understood. Especially, the question of the existence of a decoupled glass transition between the large and small population remains. In order to measure colloidal dynamics on very long time scales and to disentangle the dynamics of the two populations, we employ contrast variation multispeckle diffusing wave spectroscopy. With this method, we aim to analyze the effect of size ratio, a = r(PS)/r(pNIPAM), on particle dynamics near the glass transition of a binary colloidal system. We find that both for long-time (α−) and short-time (β−) relaxation, the dynamics of the small particles either completely decouple from the large ones (a = 0.2), moving freely through a glassy matrix, or are identical to the dynamics of the larger-sized population (a = 0.37 and 1.44). For a size ratio of 0.37, we find a single-glass transition for both particle populations. The postulated double-glass transition in simulations and theory is not observed.