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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.

The present study focused on the effects of the addition of lithium salts such as LiI, LiBr and LiCl on the rheological properties of aqueous solutions containing 15 wt% poly(vinyl alcohol) (PVA). There was a plateau in the shear storage modulus in the low frequency region, demonstrating that such solutions have a network structure attributed to hydrogen bonding of the PVA. The value of the plateau modulus evidently decreased with temperature and with the addition of lithium salts. The experimental results also demonstrated that the anion species in the salt plays an important role in determining the rheological properties, including the magnitude of the plateau modulus. The iodide anion, which is classified as a “water-structure-breaker” ion in the Hofmeister series, effectively decreased both oscillatory shear moduli including the plateau modulus. However, the effect of adding LiI decreased at high temperatures, owing to the reduced extent of hydrogen bonding.

The effect of lithium bromide (LiBr) on the structure and properties of poly (vinyl alcohol) (PVA) fibers obtained by wet-spinning was studied. The tensile modulus and strength of a PVA fiber were greatly enhanced irrespective of the post-spinning hot-stretching process. The high degree of molecular orientation arose from the reduction in the crystallinity and hydrogen bonding between PVA chains in the solution resulting from the addition of LiBr, which was revealed by the rheological properties of aqueous solutions. The LiBr was removed from the fiber during the spinning process in the coagulation bath, and during the washing process. This ensures strong hydrogen bonding in the fibers, and results in excellent mechanical properties.