Water absorption dependence of the formation of poly(vinyl alcohol)-iodine complexes for poly(vinyl alcohol) films

Poly(vinyl alcohol) (PVA) films annealed at different temperatures are used to explore the effects of the water absorption on the formation of PVA–iodine complexes. It's found that the higher the annealing temperature, the stronger the interaction force between PVA segments, and the smaller the free volume of the PVA films. These mainly lead to the reduction of the amount of PVA segments with a moderate degree of hydration (i.e., PVA segments with moderate mobility), which are the major segments participating in the formation of PVA–iodine complexes. Therefore, PVA films with higher water absorption not only possess faster complexation speed and form more PVA–iodine complexes, but also increase the proportion of polyiodide ions with a longer length. Moreover, the complexation restricts the PVA segments with high mobility, resulting in the formation of the intermolecular ordered structure. The water absorption dependence may guide the dyeing process to obtain PVA polarizers with excellent optical performance.