Stress Relaxation Mechanisms in Rubbers Reinforced with Carbon Blacks

Abstract

Abstract 1. In vulcanized rubbers containing blacks a multi-stage mechanism for stress relaxation was observed. It was discovered that the stress relaxation process consists of five fundamental processes: the first three relaxation processes, related to the slow stages of physical relaxation within the bulk of the rubber, have no connection with the fillers (“soft” domains); the fourth process has to do with the relaxation in the black-rubber domain; the fifth process involves the chemical relaxation of vulcanizates. 2. The fundamental mechanisms of the first 3 relaxation processes in the soft domains have the same activation energy values and the same segmental mechanism as the rearranged domains found in supermolecular weight structures, which are also present in unfilled vulcanizates. 3. In the investigated stress range of up to 200% elongation, the activation energy for the first 3 relaxation processes in the soft domains of filled vulcanizates is not a function of the deformation strain, whereas the activation energy of the fourth relaxation process in the black-rubber domains of filled rubbers is a function of the deformation and of the filler content. For these reasons, rubber loaded with carbon blacks, in contrast to unfilled rubbers, possess the typical nonlinearity of viscoelastic materials. 4. The activation energies of the relaxation processes in the black-rubber domains decrease in a linear fashion with the value for the initial tensile stress in filled vulcanizates, and decrease in like manner for vulcanizates containing different proportions of fillers. The kinetic units, determined from the activation energies of these processes, appeared to be segments of chains with activation energies of up to 40% more than the activation energies of the physical relaxation processes in the soft domains. The other kinetic units of the processes proved to be black particles, the dimensions of which were calculated from the values for the coefficients in the formula for relaxation time.