Linear Viscoelasticity of Weakly Hydrogen-Bonded Polymers near and below the Sol-Gel Transition

Supramolecular polymers bearing weak hydrogen bonds (sticker) can express outstanding dynamic properties due to their labile association. Studying the linear viscoelasticity (LVE) of this type of polymer can provide us with sufficient knowledge to design polymeric materials for applications that need dynamic properties such as self-healing. Using different compositions of flexible weak stickers, LVE analysis showed scalings corresponding to a transition from a linear precursor to a cluster. By introducing one sticker per repeating unit of the precursor polymer, the effect of sticker distribution along the chain as well as phase separation is excluded. However, even a fully functionalized polymer could not show any network formation, whereas surprisingly, a stable cluster was formed. This proves that weakly associated networks do not dissociate rapidly and can relax as a cluster at extended time before the dissociation of stickers can lead to the relaxation of linear analogous (slow kinetics similar to strong physical or even chemical bonds.) On the other hand, the absence of a gel even in fully sticker-functionalized polymers shows that the weakness of these polymers can be described as their weakness in complete association (thermodynamically not favored)

Relationship between linear viscoelastic properties and molecular structure for linear and branched polymers

The prediction of linear viscoelasticity (LVE) of a polymer melts from the knowledge of their structure has received tremendous attention in recent years. Quite accurate quantitative predictions are obtained for linear polymers, including inverse predictions of molecular weight distributions from knowledge of rheological response. The situation for branched polymers is much more complicated for at least two reasons. First, because of the incredible variety of architectures that can be, and are actually, made in the lab or by industry. Second, because branched polymers are characterised by very broad distributions of relaxation times, which are very dependent on details of the architecture. The main objective of this work is to propose a model suitable for predicting LVE of arbitrary mixtures of (a)symmetric stars and linear molecules, where the interrelation of relaxation processes (as reptation, tube length fluctuations or constraint release process) cannot be predicted a priori. We validate it on a large set of experimental data taken from the literature, from our own experiments or from co-workers. Next, we use it to detect long chain branching (LCB) in sparsely branched polycarbonate samples. This characterization technique, based on the analysis of the relaxation moduli, is compared to solution characterization. A similar work is performed for polyethylene samples, on which we compare our method to classical methods based on the measurement of their intrinsic viscosity or on the analysis of their activation energies spectrum. The success of our model in describing the relaxation of an already broad range of polymer structures gives some hope for understanding the dynamics of more complex systems. Indeed, its structure allows us to easily extend it to H or comb polymers and then, to proceed to polymers always closer to the industrial polymers.(FSA 3)--UCL, 200