Study of cryostructuring of polymer systems. 33. Effect of rate of chilling aqueous poly(vinyl alcohol) solutions during their freezing on physicochemical properties and porous structure of resulting cryogels

Poly(vinyl alcohol) cryogels are obtained and investigated. The cryogels are prepared by freezing an initial polymer solution (100 g/L) at chilling rates of 1.85, 0.3, 0.03, or 0.003°C/min followed by defrosting the frozen (?20°C/12 h) preparations at heating rates of 0.3, 0.03, or 0.003°C/min. It is shown that a noticeable influence of the chilling rate on the rigidity and heat endurance of the gel matrix is observed at very slow regimes of chilling (on the order of thousandths of degree centigrade per minute). One of the reasons for a reduction in the rigidity of resulting cryogels and the fusion enthalpy of the nodes in their supramolecular networks is the formation of a homo-phase hydrogel during the long-term exposure of the concentrated polymer solution to low temperatures prior to the onset of ice crystallization. The effect of the regime of chilling the polymer solution being frozen on the porous structure of cryogels resulting from the thawing of the preparations is ambiguous due to the multifactor character of this effect; therefore, in many cases, well-defined structure-property correlations are not observed.