Gelation mechanism of agarose and κ-carrageenan solutions estimated in terms of concentration fluctuation

The gelation mechanism of agarose and κ-carrageenan aqueous solutions was investigated by using polarized light scattering and X-ray diffraction techniques in terms of the liquid–liquid phase separation. When an incident beam of He–Ne gas laser was directed to the gel prepared by quenching the agarose solution, the logarithm of scattered intensity increased linearly in the initial stage and tended to deviate from this linear relationship in the latter stage. If the linear increase in the initial stage could be analyzed within the framework of the linear theory of spinodal decomposition proposed by Cahn, the phase diagram indicated that the gelation is attributed to the phase separation due to the concentration fluctuation of solution. Furthermore, in the later stage showing the deviation of the linear relationship, light scattering under Hv polarization condition showed a X-type pattern indicating the existence of optically anisotropic rods, the optical axes being parallel or perpendicular with respect to the rod axis. In spite of the existence of the rods, no crystallites were confirmed by the corresponding X-ray diffraction and DSC measurements. For κ-carrageenan solutions, the logarithm of scattered intensity against time showed a constant value. This indicated that the gelation of κ-carrageenan solutions is independent of liquid–liquid phase separation but is due to the rapid formation of cross-linking points. Accordingly it turns out that the small difference of chemical structure between agarose and κ-carrageenan causes quite different gelation mechanism.