Aging of rotational diffusion in colloidal gels and glasses.

We study the rotational diffusion of aging Laponite suspensions for a wide range of concentrations using depolarized dynamic light scattering. The measured orientational correlation functions undergo an ergodic to nonergodic transition that is characterized by a concentration-dependent ergodicity-breaking time. We find that the relaxation times associated with rotational degree of freedom as a function of waiting time, when scaled with their ergodicity-breaking time, collapse on two distinct master curves. These master curves are similar to those previously found for the translational dynamics; the two different classes of behavior were attributed to colloidal gels and glasses. Therefore, the aging dynamics of rotational degree of freedom provides another signature of the distinct dynamical behavior of colloidal gels and glasses.

Theory of supramolecular co-polymerization in a two-component system.

As a first step to understand the role of molecular or chemical polydispersity in self-assembly, we put forward a coarse-grained model that describes the spontaneous formation of quasi-linear polymers in solutions containing two self-assembling species. Our theoretical framework is based on a two-component self-assembled Ising model in which the chemical bidispersity, i.e., the presence of two distinct chemical entities, is parameterized in terms of the strengths of the binding free energies that depend on the monomer species involved in the pairing interaction. Depending upon the relative values of the binding free energies involved, different morphologies of assemblies that include both components are formed, exhibiting random, blocky or alternating ordering of the two components in the assemblies. Analyzing the model for the case of blocky ordering, which is of most practical interest, we find that the transition from conditions of minimal assembly to those characterized by strong polymerization can be described by a critical concentration that depends on the concentration ratio of the two species. Interestingly, the distribution of monomers in the assemblies is different from that in the original distribution, i.e., the ratio of the concentrations of the two components put into the system. The monomers with a smaller binding free energy are more abundant in short assemblies and monomers with a larger binding affinity are more abundant in longer assemblies. Under certain conditions the two components congregate into separate supramolecular polymeric species and in that sense phase separate. We find strong deviations from the expected growth law for supramolecular polymers even for modest amounts of a second component, provided it is chemically sufficiently distinct from the main one.

Stochastic qualifier of gel and glass transitions in laponite suspensions.

The existence of the important similarities between gelation and glass transition makes it hard to distinguish between the two types of nonergodic states experimentally. Here, we report on a stochastic analysis of the scattered light intensity through a colloidal particles suspension during the gel and glass formation. In this analysis, we exploit the methods developed for complex hierarchical systems, such as turbulence. Using the multiplicative log-normal cascade models, we provide a criterion to distinguish gels from glasses.

Multifractal analysis of light scattering-intensity fluctuations.

We provide a simple interpretation of non-Gaussian nature of the light scattering-intensity fluctuations from an aging colloidal suspension of Laponite using the multiplicative cascade model, Markovian method, and volatility correlations. The cascade model and Markovian method enable us to reproduce most of recent empirical findings: long-range volatility correlations and non-Gaussian statistics of intensity fluctuations. We provide evidence that the intensity increments Deltax(tau)=I(t+tau)-I(t), upon different delay time scales tau, can be described as a Markovian process evolving in tau. Thus, the tau dependence of the probability density function p(Deltax,tau) on the delay time scale tau can be described by a Fokker-Planck equation. We also demonstrate how drift and diffusion coefficients in the Fokker-Planck equation can be estimated directly from the data.

High-bandwidth viscoelastic properties of aging colloidal glasses and gels.

We report measurements of the frequency-dependent shear moduli of aging colloidal systems that evolve from a purely low-viscosity liquid to a predominantly elastic glass or gel. Using microrheology, we measure the local complex shear modulus G;{*}(omega) over a very wide range of frequencies (from 1Hzto100kHz ). The combined use of one- and two-particle microrheology allows us to differentiate between colloidal glasses and gels-the glass is homogenous, whereas the colloidal gel shows a considerable degree of heterogeneity on length scales larger than 0.5microm . Despite this characteristic difference, both systems exhibit similar rheological behaviors which evolve in time with aging, showing a crossover from a single-power-law frequency dependence of the viscoelastic modulus to a sum of two power laws. The crossover occurs at a time t_{0} , which defines a mechanical transition point. We found that the data acquired during the aging of different samples can be collapsed onto a single master curve by scaling the aging time with t_{0} . This raises questions about the prior interpretation of two power laws in terms of a superposition of an elastic network embedded in a viscoelastic background.

Multiple nonergodic disordered states in Laponite suspensions: a phase diagram.

We study the time evolution of different Laponite suspensions from a low-viscosity ergodic state to a viscoelastic nonergodic state over a wide range of volume fractions and salt contents. We find that the evolution of nonergodicity parameter (Debye-Waller factor) splits into two branches for all the samples, which correspond to two distinct dynamically arrested states. At moderately high salt concentrations, on the other hand, a third nonergodic state appears that is different from the above two nonergodic states. Measurement of the conductivity of Laponite solutions in pure water shows that the contribution of counterions in the ionic strength is considerable and their role should be taken into account in interpretations of aging dynamics and the phase diagram. Based on these data and available data in the literature, we propose a (nonequilibrium) phase diagram for Laponite suspensions.