Colloidal crystallization of cationic gel spheres of lightly cross-linked poly(2-vinylpyridine) in the deionized aqueous suspension

Colloidal crystallization of deionized suspensions of the cationic gel spheres of lightly cross-linked poly(2-vinylpyridine) (PEGMA-P2VP) has been studied from the microscopic observation, morphology, phase diagram, and elastic property. Critical concentrations of melting coexisted with ion-exchange resins were low compared with those without resins and increased but slightly as the degree of cross-linking decreased. The densities of the gel spheres, i.e., weight percent of the gel spheres divided by the corresponding volume percent, were between 0.7 and 0.9 and rather insensitive to the degree of cross-linking of the spheres examined from 0.1 to 1 mol%. This means that the gel spheres are rather dense. The closest inter-sphere distances of the crystals were much longer than the hydrodynamic diameters of the gel spheres especially at low sphere concentrations. Fluctuation parameters evaluated from the rigidities of the crystals of PEGMA-P2VP were similar to those of colloidal crystals of typical hard spheres. Mono-layered adsorption of cationic gel spheres at the nearest-neighbored layer from a cover glass of the cell was observed microscopically. The stable ordered layers, however, formed beyond the monolayer in the suspension phase. These experimental findings support the important role of the extended electrical double layers around the cationic gel spheres in addition to the excluded volume effect of the sphere themselves on the crystallization.