Relaxation process and dynamical heterogeneities in chemical gels: critical behavior of self-overlap and its fluctuation.

We study the dynamical behavior in chemical gelation, as the gelation threshold is approached from the sol phase. On the basis of the heterogeneous diffusion due to the cluster size distribution, as expected by the percolation theory, we predict the long time decay of the self-overlap as a power law in time t(-3/2). Moreover, under the hypothesis that the cluster diffusion coefficient decreases in size as a power law, s(-x), the fluctuation of the self-overlap, χ(4)(t), exhibits growth at short time as t((3-τ)/x), where τ is the cluster size distribution critical exponent. At longer times, χ(4)(t) decays as t(-3/2) while, at intermediate times, it reaches a maximum at time t*, which scales as s*(x), where s* is the size of the critical cluster. Finally, the value of the maximum χ(4)(t*) scales as the mean cluster size. The theoretical predictions are in agreement with molecular dynamic calculations in a model system, where spherical monomers are bonded by a finite extendable nonlinear elastic (FENE) potential.

Clusters in colloidal systems.

We study the dynamical properties of a model for charged colloidal particles, performing molecular dynamics simulations and observing the behavior of bond persistence functions, self-intermediate scattering functions at different wave vectors, and mean-square displacements of the particles, in three different regimes of the volume fraction. At the lowest volume fraction the system displays properties very similar to those of a gelling system, which can be interpreted in terms of the distribution of cluster sizes, with a peak in the dynamical susceptibility at the lowest wave vector. At the highest volume fraction, a percolating network of bonds is always present, and the system is strongly reminiscent of strong glasses, with the maximum in the dynamical susceptibility increasing when the temperature is lowered, and an Arrhenius dependence of the relaxation times. At intermediate volume fractions, a complex behavior is found, where both the distribution of cluster sizes and the intercluster correlations due to crowding are important.