Ageing of Natural Rubber under Stress

We report a dynamical-mechanical study of stress relaxation at small deformation in a natural (polyisoprene) rubber well above its glass transition temperature Tg. We find that an almost complete relaxation of stress takes place over very long relaxation periods, even though the elastic network is retained. The relaxation rate and the long-time equilibrium modulus are sensitive functions of temperature which do not follow time-temperature superposition. Many characteristic features of non-ergodic ageing response are apparent at both short and very long times. We interpret the observed behaviour in terms of the nature of rubber crosslinks, capable of isomerisation under stress, and relate the results to recent models of slow