Chain orientation in natural rubber, Part I: the inverse yielding effect.

Inhomogeneous deformations are observed in stretched natural rubber of different crosslink density; the conditions of observation, nucleation and propagation are given in the first part of the paper. In samples of low crosslink density these inhomogeneities recall necking observed in others materials and in glassy polymers when the materials are drawn above a critical draw ratio. The difference is that in natural rubbers, NR, they nucleate and propagate at constant stress during unloading. This phenomenon, called inverse yielding appears during recovery only if the samples have been drawn previously in the hardening domain. During necking propagation the stress is constant. The mechanical and crystallinity properties of samples with and without inverse yielding are studied as a function of draw ratio, crosslink density and temperature. In the second part of the paper this transition zone (neck) of thickness 2 mm is studied by WAXS at the synchrotron source. From the orientation of NR crystallites and from the orientation of the stearic acid (2%, present in this type of rubber) we conclude that the deformation in the neck follows the flow lines. From the local crystallinity of the NR crystallites one deduces the local draw ratio across this transition zone. We suggest that in all these rubbers, which present a plateau of the recovery stress strain curve, micronecking exists. This effect is discussed in the framework of the Flory theory.