Application of the Hofmeister series to the structure and properties of poly(vinyl alcohol) films containing metal salts

Abstract

The effects of ions on the structures and properties of poly(vinyl alcohol) films were systematically studied using various metal salts. Although cations play an important role, the data obtained in this study demonstrated that the strong ion–dipole interactions between anions and poly(vinyl alcohol) chains also have a significant impact on crystallinity and glass transition temperature. For the first time, the study revealed that the impact of the added salts follows the Hofmeister series. Investigations of various bromine salt cations revealed that Li+ is more effective at disrupting the water structure than either Na+ or K+. Further experiments using lithium salts with various anion species verified that lithium salts play an important role in determining the crystallinity and hydrogen bonding within aqueous poly(vinyl alcohol) and therefore affect the dynamic mechanical properties of films. This phenomenon clearly follows the order LiClO4 > LiI > LiBr > LiNO3 > LiCl, which corresponds to the Hofmeister series. The salt addition affects the structure and properties of poly(vinyl alcohol) films as it reduces the hydrogen bonding in PVA chains and decreases the crystallinity. Consequently, the Tg shifts to low temperatures, and the modulus beyond Tg decreases markedly. This study confirmed that the impact of bromine salts on the structure and properties followed the order of Hofmeister series, i.e., Li+ > Na+  > K+. Although cations play an important role, the data obtained also demonstrated that the strong ion–dipole interactions between anions and PVA chains have a significant impact on the crystallinity and Tg.