General nonlinear rheological behavior of associative polymers

Abstract

Shear thickening is very common in telechelic associative polymers. Yet, it is not a universal characteristic of the whole class of associative polymers. Here, more general features of associative behavior are investigated. In particular, nonlinear rheological properties have been studied for both associative hydrophobically modified ethoxylated urethanes and hydrophobically modified alkali-soluble emulsions (HASE) polymers. A known common characteristic is the failure of the Cox-Merz rule for the viscosities. The equivalent relation for the first normal stress is examined here, a parallelism with the results for the viscosities has been observed. More pronounced similarities between telechelics and the more complex HASE systems can be seen in some other nonlinear properties. The dynamic moduli display strain hardening for both moduli at intermediate strains at all but the lowest frequencies, even when no shear thickening can be detected in steady state shear flow. The linear relaxation functions differ quite strongly among associative polymers. However, they all display a specific non-linear relaxation. It includes short time strain hardening followed by strain softening starting at long relaxation times. The results indicate that the same microstructural mechanisms are responsible for the rheological behavior of both classes of associative polymer.