Difference in concentration dependence of relaxation critical exponent n for alginate solutions at sol-gel transition induced by calcium cations

The sol-gel transition in aqueous alginate solutions induced by chelation with calcium cations from in situ release has been investigated with viscoelastic methods. Two alginate samples having different molecular weights (MW) were used over the concentration C-Alg of 2 similar to 6 wt % with different mole ratio f of Ca2+ to the alginate repeat unit. The gel pointf(gel) and relaxation critical exponent n were determined according to Winter's criterion, the later agrees well with that obtained from the relaxation modulus. The results indicate that the power law is valid for the dynamic relaxation at the gel point and the critical gel possesses the self-similarity in structure. With increasing C-Alg, f(gel) for the alginate with lower MW decreases dramatically and n is almost constant of about 0.71. In contrast, f(gel) for the higher MW alginate with is almost a constant and n decreases from 0.72 then levels off at 0.37 with increasing C-Alg, indicating that the concentration dependence of n varies with MW of alginate in the starting solution. The fractal dimension d(f) estimated from n suggests a denser structure in the critical gel of higher MW alginate. Either n or df has been found to follow one curve for the two samples if plotted against the number of cross-link junctions per polymer chain, which is proportional to the alginate MW.