Rheological Study of Transient Networks with Junctions of Limited Multiplicity

TL;DR

This paper develops a theoretical model for transient polymer networks with variable junction multiplicity, analyzing how rheological properties depend on association equilibrium, concentration, and temperature.

Contribution

It extends classical transient network theories by incorporating correlations among chains and variable junction multiplicity, providing new insights into rheological behavior.

Findings

Dynamic shear moduli follow a Maxwell model with a single relaxation time.

Plateau modulus and viscosity increase nonlinearly with concentration at low levels.

Relaxation time grows with concentration due to pairwise junctions.

Abstract

Viscoelastic and thermodynamic properties of transient gels comprised of telechelic polymers are theoretically studied. We extend classical theories of transient networks so that correlations among polymer chains through the network junctions are taken into account. This extension enables us to investigate how rheological quantities, such as viscosity and elastic modulus, are affected by the association equilibrium conditions, and how these quantities are related to the aggregation number of junctions. We present a theoretical model of transient networks with junctions comprised of variable number of hydrophobic groups on the chain ends. Elastically effective chains are defined as the chains whose both ends are associated with end groups on other chains. It is shown that the dynamic shear moduli are well described in terms of the Maxwell model characterized by a single relaxation time and the high-frequency plateau modulus as in the classical theories, but the reduced dynamic shear moduli depend on the polymer concentration and temperature through the reduced concentration c given as a combination of the association constant and the volume fraction of end groups. The plateau modulus and the zero-shear viscosity rise nonlinearly with increasing c when c is small, but they are proportional to c for higher c. The relaxation time also increases as c increases due to the presence of pairwise junctions at small c.