Viscoelastic properties of physically crosslinked networks. I: Non-linear stationary viscoelasticity (Q1199369)

The paper employs a model network made up of polymer chains carrying reactive groups at the ends, with junctions arising from the reversible association of the end groups, and examines the stationary state solutions of the fundamental equation governing the time development of the number of elastically active chains under macrodeformation to obtain a quantitative description of the dynamical properties of thermo- reversible gels. Shear flow with constant shear rate \(\dot\gamma\) and elongational flow with constant elongational rate \(\dot\varepsilon\) are analyzed and it is seen that the stationary properties depend sensitively on the chain breakage function \(\beta(r)\) as well as the chain recombination probability \(p\). The choice \(\beta(r)=\beta_ 0\exp kr\) is proposed, where \(\beta_ 0\) and \(k\) are functions of the temperature \(T\) and the molecular weight of the polymer chain. The stationary viscoelastic properties exhibit an exponential dependence on \(T\) for the above choice of the breakage function. Thickening and thinning conditions for both types of flow are examined and it is seen that the parabolic choice of \(\beta(r)\) allows rigorous calculations of the viscoelastic properties of the network.