Relaxation processes in vulcanized rubber. II. Secondary relaxation due to network breakdown

An experimental study is described of a “secondary” relaxation process in stretched vulcanizates, which becomes dominant after long periods at normal temperatures. It is shown to be affected markedly by the temperature, the atmosphere in which the test is conducted, and the presence of oxidation inhibitors. It is therefore attributed to oxidative deterioration of the molecular structure. In some vulcanizates, however, a similar or even greater relaxation is found to occur in vacuo, and this is attributed to the failure of specific crosslink structures. The extent of recovery on releasing the extended test pieces has also been investigated for a number of natural rubber vulcanizates.