Poly(vinyl alcohol) cast gels (PVA cast gels) were prepared at different gelation temperatures, T gel , and the swelling ratio and mechanical properties were characterized by the equilibrium weight measurement, a uniaxial loading test, a tearing force measurement, and a cyclic compression test at room temperature. The results showed that the swelling ratio decreased and both the breaking stress and the tearing energy increased with an increase in T gel . The compression deformation energy of 50% reduction of its original size increased monotonically, while the hysteresis loss was not affected by T gel . To understand these macroscopic properties, the network structures of the samples were examined by X-ray diffraction and Fourier transform infrared measurements. As a result, the size of the microcrystallites increased with an increase in T gel and the average distance between the microcrystallites also increased. These results suggested that the structures of PVA networks, crosslinked by the microcrystallites, have essential roles in determining the mechanical properties of PVA cast gels. The macroscopic mechanical properties are discussed on the basis of the size, number, and distribution of microcrystallites as crosslinkers and the homogeneity of amorphous PVA networks, which were determined at gelation. Experimental procedure Sample preparationPVA powder was kindly supplied by Kuraray Co., Ltd. (cat. no. PVA117), and was used without further purification. The

Poly(vinyl alcohol) (PVA) gels can be easily prepared by either the freeze‐thawing (FT gel) method or by the cast‐drying (CD gel) method. Although the resulting nanostructured networks of the FT and CD gels are similar, their physical properties are quite different; while CD gels are transparent and elastic, FT gels are opaque and less elastic. Moreover, the tear energy of the FT gels is much greater than that of the CD gels, which is a direct result of micrometer‐scale differences in their network structures. In order to control the distribution of microcrystallites on nano‐ and micrometer scales, FT gels were prepared from PVA solutions with different water contents. As a result, the gel gradually became more transparent as the initial water content was decreased; and accordingly, the tear energy decreased. Tear resistance was improved in the case of FT gels by repeating the number of FT cycles, whereas with CD gels, this was achieved by increasing the gelation temperature. These results indicate that the microscopic network structures are characterized by a micrometer‐scale bundled‐polymer (fibril), which determines the tear energy of FT gels. Simple methods to control the fibril network structure of FT gels using a unidirectional freezing method are presented herein, with the swelling and mechanical properties of modified FT gels discussed in terms of their multiple‐scale network structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41356.