Dielectric properties of PVA cryogels prepared by freeze-thaw cycling.

Solutions of polyvinyl alcohol (PVA) in water can form gels upon repeated freezing and thawing. These PVA cryogels have applications as biomaterials, including artificial tissue and drug delivery systems. We have studied the dielectric properties of PVA cryogels within the freeze-thaw cycles as a function of both frequency and temperature in order to understand the physical changes that take place during the thermal cycling process. Our results indicate that most of the changes in dielectric properties occur during the cooling phase of the first cycle and suggest that the solution must be cooled below a critical temperature of about 263 K for the formation of a gel that persists after thawing. The material's dielectric spectrum shows the presence of several relaxation processes. We identify one of these with the dielectric relaxation of ice and two others with motions of the PVA polymer chains. The temperature dependence of the polymeric relaxation times suggests that they are both thermally activated, with an activation energy of roughly 300 kJ/mol.

Supercooling and Nucleation of Fatty Acids: Influence of Thermal History on the Behavior of the Liquid Phase.

Saturated fatty acids are an exceptionally important class of liquids, used in many consumer products and suggested as phase change materials (PCMs) for thermal energy storage, in part because they crystallize with minimal supercooling. Here we investigate fatty acid nucleation to understand why crystallization is so facile, as a step toward identifying potential mechanisms for the suppression of supercooling in other PCMs. We find that fatty acid supercooling can be induced only if the liquid is first heated above a material-dependent threshold temperature. NMR spin-lattice relaxation time studies show that the average mobility of the alkyl chains in the fatty acids increases more rapidly with temperature above the supercooling threshold temperature, and NMR T1 hysteresis also sets in at that temperature. Measurements of the real portion of the dielectric constant as a function of temperature show that a liquid fatty acid heated far above its melting point behaves with an apparent temperature upon cooling that is higher than the actual temperature, when compared to its behavior at the same temperature upon heating. Our results suggest that molecular clusters in the liquid fatty acids break apart when the liquids are heated above their threshold temperature and do not immediately re-form on cooling. The breakup of clusters leads to an increase in the mobility of the fatty acid molecules. Because the clusters do not re-form quickly on subsequent cooling, nucleation does not occur, and substantial supercooling results.