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.