Understanding the molecular origin of shear thinning in associative polymers through quantification of bond dissociation under shear

Abstract

Understanding the physics of associative polymers is often limited by our inability to directly measure bond dissociation under deformation. In this work, we developed a rheo-fluorescence technique and applied it to characterize the nonlinear shear response of linear side-functionalized polymer chains cross-linked via nickel-terpyridine complexation. As the network was sheared, the fraction of dissociated bonds was quantitatively measured based upon a change in fluorescence with metal dissociation. Shear thinning of the gel was accompanied by only a small increase in the fraction of dissociated bonds. Comparison with several transient network models shows that the shear thinning within the constraint of the measured fraction of dissociated bonds cannot be explained by classical theories that include retraction of dangling chains alone; the rheological response likely involves alternative modes of stress relaxation.