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

[Image: see text] The network structure of poly(vinyl alcohol) (PVA) hydrogels obtained by freezing−thawing cycles was investigated by solid-state (1)H low-field NMR spectroscopy. By the application of multiple-quantum NMR experiments, we obtain information about the segmental order parameter, which is directly related to the restrictions on chain motion (cross-links) formed upon gelation. These measurements indicate that the network mesh size as well as the relative amount of nonelastic defects (i.e., non-cross-linked chains, dangling chains, loops) decrease with the number of freezing−thawing cycles but are independent of the polymer concentration. The formation of the PVA network is accompanied by an increasing fraction of polymer with fast magnetization decay (∼20 μs). The quantitative study of this rigid phase with a specific refocusing pulse sequence shows that it is composed of a primary crystalline polymer phase (∼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 do 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 ∼80 °C leads to the destruction of the network gel and the formation of an isotropic PVA solution.