The nonlinear viscoelastic response of carbon black-filled natural rubbers

Three series of tensile relaxation tests are performed on natural rubber filled with various amounts of carbon black. The elongation ratio varies in the range from λ = 2.0 to 3.5. Constitutive equations are derived for the nonlinear viscoelastic behavior of filled elastomers. Applying a homogenization method, we model a particle-reinforced rubber as a transient network of macromolecules bridged by junctions (physical and chemical cross-links, entanglements and filler clusters). The network is assumed to be strongly heterogeneous at the meso-level: it consists of passive regions, where rearrangement of chains is prevented by surrounding macromolecules and filler particles, and active domains, where active chains separate from temporary nodes and dangling chains merge with the network as they are thermally agitated. The rate of rearrangement obeys the Eyring equation, where different active meso-domains are characterized by different activation energies. Stress-strain relations for a particle-reinforced elastomer are derived by using the laws of thermodynamics. Adjustable parameters in the constitutive equations are found by fitting experimental data. It is demonstrated that the filler content strongly affects the rearrangement process: the attempt rate for separation of strands from temporary nodes increases with elongation ratio at low fractions of carbon black (below the percolation threshold) and decreases with λ at high concentrations of filler.