Stress-strain relations and molecular orientation in highly crosslinked cis-polyisoprene networks

Results of equilibrium stress-strain experiments and Fourier transform infra-red measurements of segmental orientation, previously reported for moderately crosslinked cis-polyisoprene networks by Amram et al. (Polymer 1986, 27, 877), are extended to networks with high degrees of crosslinking. The samples were stretched to the limit of maximum chain extensibility. The absence of strain-induced crystallization during experiments was inferred from infra-red measurements, according to which the 844 cm^-1 absorption band specific to crystalline regions did not exhibit any systematic shift in one direction. The reduced force versus inverse extension ratio showed strong upturns while the reduced orientation curves did not exhibit any upturns. Likewise, the analogue of the stress optical coefficient, defined as the ratio of molecular orientation to true stress, exhibited a strong decrease with extension, in contrast to Gaussian networks in which it is approximately independent of the degree of deformation.