Physical aging and compressed exponential behaviors in a model soft colloidal system.

Diffusing wave spectroscopy (DWS)-based micro-rheology has been used in different optical geometries (backscattering and transmission) as well as different sample thicknesses in order to probe system dynamics at different length scales [D. J. Pine, D. A. Weitz, J. X. Zhu, E. Herbolzheimer. J. Phys., 1990, 51(18), 2101-2127]. Previous study from this lab [Q. Li, X. Peng, G. B. McKenna. Soft Matter, 2017, 13(7), 1396-1404] indicates the DWS-based micro-rheology observes the system non-equilibrium behaviors differently from macro-rheology. The object of the present work was to further explore the non-equilibrium dynamics and to address the range of utility of DWS as a micro-rheological method. A thermo-sensitive core-shell colloidal system was investigated both during aging and subsequent to aging into a metastable equilibrium state using temperature-jump induced volume fraction-jump experiments. We find that in the non-equilibrium state, significant differences in the measured dynamics are observed for the different geometries and length scales. Compressed exponential relaxations for the autocorrelation function g2(t) were observed for large length scales. However, upon converting the g2(t) data to the mean square displacement (MSD), such differences with length scale diminished and the long-time MSD behavior was consistent with diffusive behavior. These observations in the non-equilibrium behaviors for different length scales leads to questioning of some interpretations in the current field of light scattering-based micro-rheology and provides a possibility to interrogate the aging mechanisms in colloidal glasses from a broader perspective than normally considered in measurements of g2(t) using DWS-based micro-rheology.