Structure of Thermoreversible Poly(vinyl alcohol) Cryo-Hydrogels as studied by Proton Low Field NMR Spectroscopy

Abstract

The network structure of Poly(vinyl alcohol) (PVA) hydrogels obtained by freezing-thawing cycles was investigated by solid state 1H low field NMR spectroscopy. By application of multiple-quantum NMR experiments, we obtain information about the segmental order parameter, which is directly related to the restrictions to chain motion (crosslinks) formed upon gelation. These measurements indicate that the network mesh size, as well as the relative amount of non-elastic defects (i.e. non-crosslinked chains, dangling chains, loops) decreases with the number of freezing-thawing cycles, but it is independent of the polymer concentration. The formation of the PVA network is accompanied by an increasing fraction of polymer with fast magnetization decay (∼20μs). The quantitative study of this rigid phase with a specific refocusing pulse sequence shows that it is composed of a primary crystalline polymer phase (around 5%), which constitutes the main support of the network structure and determines the mesh size, and a secondary population of more imperfect crystallites, which increase the number of elastic chain segments in the polymer gel but does not affect the average network mesh size appreciably. Correspondingly, progressive melting of the secondary crystallites with increasing temperature does not affect the network mesh size but only the amount of network defects, and melting of the main PVA crystallites at around 80 ºC leads to destruction of the network gel and formation of an isotropic PVA solution.