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Non-equilibrium relaxation and near-arrest dynamics in colloidal suspensions

M Medina-Noyola and Pedro Ramírez-González

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In this work we propose a theory to describe the irreversible diffusive relaxation of the local concentration of a colloidal dispersion that proceeds toward its stable thermodynamic equilibrium state, but which may in the process be trapped in metastable or dynamically arrested states. The central assumption of this theory is that the irreversible relaxation of the macroscopically observed mean value \bar {n}(\mathbf
{r},t) of the local concentration of colloidal particles is described by a diffusion equation involving a local mobility b*(r,t) that depends not only on the mean value \bar {n}(\mathbf {r},t) but also on the covariance \sigma (\mathbf {r},\mathbf {r}';t)\equiv \overline
{\delta n(\mathbf {r},t)\delta n(\mathbf {r}',t)} of the fluctuations \delta n(\mathbf {r},t) \equiv n(\mathbf {r},t)-\bar {
n}(\mathbf {r},t) . This diffusion equation must hence be solved simultaneously with the relaxation equation for the covariance σ(r,r';t), and here we also derive the corresponding relaxation equation. The dependence of the local mobility b*(r,t) on the mean value and the covariance is determined by a self-consistent set of equations involving now the spatially and temporally non-local time-dependent correlation functions, which in a uniform system in equilibrium reduces to the self-consistent generalized Langevin equation (SCGLE) theory of colloid dynamics. The resulting general theory considers the possibility that these relaxation processes occur under the influence of external fields, such as gravitational forces acting in the process of sedimentation. In this paper, however, we describe a simpler application, in which the system remains spatially uniform during the irreversible relaxation process, and discuss the general features of the glass transition scenario predicted by this non-equilibrium theory.


PACS

82.70.Dd Colloids

66.10.C- Diffusion and thermal diffusion

65.20.-w Thermal properties of liquids

82.70.Kj Emulsions and suspensions

Subjects

Soft matter, liquids and polymers

Chemical physics and physical chemistry

Dates

Issue 50 (16 December 2009)

Received 1 June 2009, in final form 14 June 2009

Published 23 November 2009



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