Time-Ionic Strength Superposition: A Unified Description of Chain Relaxation Dynamics in Polyelectrolyte Complexes

Addition of salt speeds up chain relaxation dynamics in polyelectrolyte complexes (PECs), and time-salt superposition (TSS) approaches to describe the linear viscoelastic response of PECs are well-established. However, TSS is carried out at fixed initial polyelectrolyte concentrations, and varying the initial polyelectrolyte concentration results in distinct TSS master curves. In this contribution, we show that accounting for the small ions that accompany the oppositely charged polyelectrolyte chains (designated as accompanying counterions) enables assimilation of these distinct TSS master curves into a single universal master curve. This approach, that we christen as time-ionic strength superposition (TISS), enables a unified description of the PEG viscoelastic response in terms of the solution ionic strength, that accounts for both the accompanying counterions and the added ions, and underlines the dynamic similarities between PECs and semidilute polymer solutions. The sticky electrostatic associations among the oppositely charged chains, however, contribute additional relaxation modes in the PECs. We demonstrate that the time scales of these additional relaxation modes are described quantitatively by a modified sticky Rouse model that accounts for the influence of solution ionic strength on electrostatic screening and chain friction.