In
this study, we examined the structure, linear viscoelastic (LVE)
properties, and nonlinear shear and elongational properties of unentangled
telechelic ionomers based on either sodium carboxylate or sodium sulfonate
groups, coded as M
n-COONa and M
n-SO3Na, with the number-average
molecular weight M
n varying from 5 to
16 kg mol–1. A combination of X-ray scattering and
LVE data revealed that both types of ionomers form networks sustained
by “superbridges” transiently cross-linked by salt aggregates.
The aggregates were found to be more stabilized in the M
n-SO3Na ionomers than in the M
n-COONa ionomers. In addition, the X-ray scattering and
LVE data suggested that the inner and end aggregates of the superbridge
are equally stabilized in M
n-SO3Na, while the end aggregates are more stable in M
n-COONa. This difference in the aggregate stability in
the two series of ionomers was found to have a significant effect
on nonlinear rheology; namely, under the shear or elongational flow
fields with the Weissenberg number Wi > 1, M
n-COONa showed a larger strain on the stress
overshoot compared to M
n-SO3Na. This result suggested that the M
n-COONa ionomers can better adjust the network under flow before the
overshoot. After the overshoot, the weaker pseudo-yielding and higher
fracture strains were attained for M
n-COONa,
suggesting that the associated network can be reconstructed more easily
for M
n-COONa. All these features are attributable
to a nonuniform distribution of the salt aggregate size and superbridge
length of M
n-COONa, which enables more
efficient energy dissipation under strong flow through fast rearrangement
of the network.