ABSTRACT
Potential gravity-induced deformations of polyacrylamide matrices during gelling were investigated in two different initiator systems based on (i) photopolymerization with 100 microM methylene blue, 1 mM sodium toluene sulfinate (reducer) and 50 microM diphenyliodonium chloride (oxidizer) (photopolymerization) and (ii) chemical polymerization, utilizing the standard persulfate N,N,N',N'-tetramethylethylenediamine. In both systems, it is seen that convective flows are imprinted in the final gel structure above a critical gelling layer thickness, set at ca. 3 mm. In both systems, progressive increments of the solution density, from normodense (density = 1.0) up to isodense with the growing polymer chains (density = 1.3) do not inhibit the appearance of strong convective flows. However, gel inhomogeneities are completely abolished even in 10 mm gelling layers if polymerization is performed in presence of density gradients, notably of sucrose, from 0 to 20%, 0 to 40% and 0 to 60%. Even the shallower gradient (0-20% sucrose) is able to completely abolish convective flows in persulfate-driven polymerization. It is hypothesized that such disturbances are not created by sedimentation of the growing polymer chains in the gravitational field, but are produced by the reaction exothermality, which produces strong buoyancy-driven flows. It is additionally demonstrated that persulfate polymerization is sensitive to oxygen absorbed from the top liquid layers, which should be carefully protected by an overlay of organic solvent. Methylene blue-induced polymerization appears to offer a series of unique advantages over chemical initiation with persulfate.
