Kinetics of anisotropic ordering in Laponite dispersions induced by a water-air interface

Abstract

In this work, we report the kinetics of ordering occurring at the water-air interface of Laponite dispersions. Propagation of such ordering into the bulk and its relaxation dynamics were systematically studied through light scattering measurements. Depolarization ratio D(p), which accounted for the optical anisotropy, was measured as a function of depth from the interface and aging of the samples. The extent of spatial ordering was found to be several decades larger than the typical particle size. Spatial ordering originated from the interface and percolated into the bulk with aging time t(w). Growth in D(p) with waiting time was found to follow power-law behavior given as D(p)~t(w)(n), with n increasing from 0.1 to 4 as one moved away from the interface into the bulk. D(p) decreased exponentially with depth h given as D(p)~e(-(h/h(0))), where h(0) is the decay length, increasing from 0.4 to 0.75 mm with aging time. Dynamic structure factor measurements performed on the samples at various aging times, depths, and temperatures yielded two distinct relaxation times: one fast mode followed by a slow mode. The fast mode remained invariant while slow mode relaxation time followed an exponential decay with depth. This study indicated that the arrested phase nucleated from the interface and propagated into the bulk, which was not observed when the surface was insulated with a layer of hydrophobic liquid. Dilution of the concentrated samples destroyed the aforesaid ordering and made the dispersion homogeneous implying the ordered state was a glass.