Theory of relaxation spectra and dielectric relaxation of rigid rodlike particles incorporated in a polymer network

Abstract

The theory of molecular mobility and relaxation spectra is developed for rodlike particles embedded in a polymer network with allowance for the involvement of the particles in collective network dynamics through topological entanglements with network fragments. A regular cubic coarse-grained network model is used, where the motion of junctions describes the mobility of large fragments (domains) of the initial network with a size equal to the distance between adjacent rodlike particles. The involvement of the rods in collective network dynamics is taken into account by introducing an effective quasi-elastic potential acting between the rods and junctions of the coarse-grained network and preventing long-distance diffusion of the embedded particles. The viscoelastic parameters of the coarse-grained (“renormalized”) network are functions of the viscoelastic characteristics of the initial network. The relaxation time spectra are calculated as well as the frequency dependences of the dielectric loss factor of the embedded particles that possess a permanent dipole moment directed along the major axis of each rod. Depending on the ratio between the viscoelastic characteristics of the rods and the network, the frequency dependence of the dielectric loss factor may have two maxima. The high-frequency maximum corresponds to local orientational movements of particles at fixed junctions of the coarse-grained network, which correspond to the position of the domain centers in the initial network. The low-frequency maximum corresponds to movements of particles involved in large-scale dynamics of network fragments. The dependence of the dielectric loss factor on the ratio between the viscoelastic parameters of the rods and the network is studied.