Telechelic Polymer Hydrogels: Relation between the Microscopic Dynamics and Macroscopic Viscoelastic Response

Telechelic polymers, that is, hydrophilic polymers with hydrophobic end-groups, spontaneously form hydrogels consisting of interconnected micelles. Here we investigate the relation between the microscopic dynamics determining the connectivity, that is, the lifetime of the physical bonds and the resulting rheological properties. This is achieved by quantitatively relating the chain exchange kinetics measured by time-resolved small-angle neutron scattering (TR-SANS) and the mechanical response obtained from linear oscillatory shear measurements. The results show that the characteristic relaxation time obtained from rheology coincides exactly with TR-SANS at intermediate concentrations. The activation energy, E_a, is concentration-independent and remain exactly the same as for TR-SANS. Upon crossing the melting point, a discrete change in activation energy is observed showing the contribution from the enthalpy of fusion to the release/debridging process. The results clearly show that the mechanical response and connectivity indeed are controlled by molecular exchange processes. The relaxation time at the lowest concentration is found to be faster in rheology as compared to TR-SANS, which can be quantitatively attributed to entropic forces arising from conformational deformation of bridging chains.