Role of Salt and Water in the Plasticization of PDAC/PSS Polyelectrolyte Assemblies

In this work, we investigate the effect of salt and water on plasticization and thermal properties of hydrated poly(diallyldimethylammonium chloride) (PDAC) and poly(sodium 4-styrenesulfonate) (PSS) assemblies via molecular dynamics simulations and modulated differential scanning calorimetry (MDSC). Commonly, both water and salt are considered to be plasticizers of hydrated polyelectrolyte assemblies. However, the simulation results presented here show that while water has a plasticizing effect, salt can also have an opposite effect on the PE assemblies. On one hand, the presence of salt ions provides additional free volume for chain motion and weakens PDAC-PSS ion pairing due to electrostatic screening, which contributes toward plasticization of the complex. On the other hand, salt ions bind water in their hydration shells, which decreases water mobility and reduces the plasticization by hydration. Our MDSC results connect the findings to macroscopic PE plasticization and the glass-transition-like thermal transition T_tr under controlled PE hydration and salt content. This work identifies and characterizes the dual nature of salt both as plasticizer and hardener of PE assemblies and maps the interconnection of the influence of salt with the degree of hydration in the system. Our findings provide insight into the existing literature data, bear fundamental significance in understanding of hydrated polyelectrolyte assemblies, and suggest a direct means to tailor the mechanical characteristics of PE assemblies via interplay of water and salt.