Hydration, Ion Distribution, and Ionic Network Formation in Sulfonated Poly(arylene ether sulfones)

TL;DR

This study uses molecular dynamics simulations to analyze hydration, ion distribution, and ionic network formation in sulfonated polysulfones, revealing how ion spacing and aggregation influence ion transport properties.

Contribution

It provides new insights into ion interactions and aggregation in sulfonated polysulfones, combining simulations with Manning's theory for better understanding.

Findings

Ions exhibit similar hydration levels as in saturated aqueous solutions.

Sulfonate ions form fibrillar aggregates at sub-saturation water contents.

Theoretical estimates of counterion condensation align with simulation results.

Abstract

We use molecular dynamics simulations to probe hydration, ion spacing, and cation-anion interaction in two sulfonated polysulfones with different ion distributions along the polymer backbone. At room temperature, these polymers remain in a glassy state even with water contents more than 10%. At the equilibrium water uptake, the ions exhibit a similar level of hydration as they would in their saturated aqueous solution. The framework of Manning's limiting law for counterion condensation is used to examine ionic interactions in the simulated polysulfones. The dielectric constant that the ions experience can be well approximated by a volume-weighted average of the dielectric constants of the polymer backbone and water. Our results show that a reasonable estimate of the average inter-ion distance, b, is obtained by using the distance where the sulfonate-sulfonate coordination number reaches 1. The spacing of the sulfonate ions along the polysulfone backbone plays a role in determining their spatial distribution inside the hydrated polymer. As a result, the value of b is slightly larger for polymers where the sulfonate ions are more evenly spaced along the backbone, which is consistent with experimental evidence. The simulations reveal that the sulfonate ions and sodium counterions form fibrillar aggregates at water contents below the equilibrium water uptake. Such extensive ionic aggregates are expected to facilitate ion transport in sulfonated polysulfone membranes, without the need for long-range chain motion as in the case of traditional rubbery ionic polymers. Our estimates for the dielectric constant and b are used in conjunction with Manning's theory to estimate the fraction of counterions condensed to the fixed ions. The prediction of Manning's theory agrees well with the simulation result.