Structure and properties of poly(vinyl alcohol) hydrogels obtained by freeze/thaw techniques

TitleStructure and properties of poly(vinyl alcohol) hydrogels obtained by freeze/thaw techniques
Publication TypeArticolo su Rivista peer-reviewed
Year of Publication2005
AuthorsRicciardi, Rosa, Auriemma F., and De Rosa C.
JournalMacromolecular Symposia
KeywordsAging of materials, Crystal structure, Crystallinity, Elastic moduli, Freeze/thaw technique, freezing, Hydration, Hydrogels, Neutron diffraction, Polyvinyl alcohols, Small angle neutron scattering (SANS0, Solvents, Structural organization, thawing, Viscoplasticity, X ray diffraction analysis

The relationships between the structure and the viscoelastic properties of freeze/thaw PVA hydrogels obtained by repeatedly freezing and thawing dilute solutions of PVA in D2O(11% w/w PVA) in as-prepared and rehydrated states are investigated. Our results indicate that the PVA chains and solvent molecules are organized at different hierarchical length scales, which include the presence of micro-and macro-pores, into a network scaffolding. The porous network is ensured by the presence of crystallites, which act as knots interconnected by portions of PVA chains swollen by the solvent. X-ray diffraction and SANS techniques are used to obtain structural information at short (angstroms) and medium (nanometers) ranges of length scales, concerning the crystallinity, the size of small crystalline aggregates and the average distance between crystallites in PVA hydrogels. Indirect information concerning the structural organization on the large length scales (microns) are provided by viscoelastic measurements. The dynamic shear elastic moduli at low frequency and low strain amplitude, G', are determined and related to the degree of crystallinity. These data indicate that a minimum crystallinity of 1% is required for these PVA samples to exhibit gel behaviour and have allowed obtaining the order of magnitude of the average mesh size in these gels. Finally, it is shown that the negative effect of aging, inducing worse physical and mechanical properties in these systems, may be prevented using a drying/re-hydration protocol able to keep the physical properties of the as-prepared PVA hydrogels. © 2005 WILEY-VCH Verlag GmbH & KGaA, Weinheim.


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