RESUMO
The time-dependent stress relaxation for a Rouse model of a cross-linked polymer melt is completely determined by the spectrum of eigenvalues of the connectivity matrix. The latter has been computed analytically for a mean-field distribution of cross-links. It shows a Lifshitz tail for small eigenvalues and all concentrations below the percolation threshold, giving rise to a stretched exponential decay of the stress relaxation function in the sol phase. At the critical point the density of states is finite for small eigenvalues, resulting in a logarithmic divergence of the viscosity and an algebraic decay of the stress relaxation function. Numerical diagonalization of the connectivity matrix supports the analytical findings and has furthermore been applied to cluster statistics corresponding to random bond percolation in two and three dimensions.
RESUMO
Shear relaxation and dynamic density fluctuations are studied within a Rouse model, generalized to include the effects of permanent random crosslinks. We derive an exact correspondence between the static shear viscosity and the resistance of a random resistor network. This relation allows us to compute the static shear viscosity exactly for uncorrelated crosslinks. For more general percolation models, which are amenable to a scaling description, it yields the scaling relation k=straight phi-beta for the critical exponent of the shear viscosity. Here beta is the thermal exponent for the gel fraction, and straight phi is the crossover exponent of the resistor network. The results on the shear viscosity are also used in deriving upper and lower bounds on the incoherent scattering function in the long-time limit, thereby corroborating previous results.
RESUMO
Molecular dynamics simulations are used to generate an ensemble of saddles of the potential energy of a Lennard-Jones liquid. Classifying all extrema by their potential energy u and number of unstable directions k, a well-defined relation k(u) is revealed. The degree of instability of typical stationary points vanishes at a threshold potential energy u(th), which lies above the energy of the lowest glassy minima of the system. The energies of the inherent states, as obtained by the Stillinger-Weber method, approach u(th) at a temperature close to the mode-coupling transition temperature T(c).