Institution: | a Department of Physics and Mathematics, Norwegian Biopolymer Laboratory, University of Trondheim, NTH, N-7034, Trondheim, Norway b Division of Biotechnology, Norwegian Biopolymer Laboratory, University of Trondheim, NTH, N-7034, Trondheim, Norway |
Abstract: | In-situ gelation of semidilute xanthan solutions with trivalent chromium, aluminum or iron ions was studied by rheology and UV-spectroscopy. Measurements of the elastic modulus of xanthan gel cylinders prepared by dialysis against the complexing ion at pH values from 2 to 6 indicate that monomeric species of the ion are ineffective, whereas dimeric or higher oligomeric species are effective in crosslinking the polysaccharide. When chromium was used as the crosslinking species, the dependence of the gelation rate on the ionic concentration followed a power law with a coefficient of 1·7. The gelation time and the gelation rate were found to extrapolate to zero at 1 m
Cr for 2·5 mg/ml xanthan. The limiting concentration of xanthan needed for gelation with 5 m
Cr(III) at 20°C was estimated as 0·35 mg/ml. This critical xanthan concentration is close to the overlap concentration c* estimated from the experimentally determined intrinsic viscosity η] using c* = 1·4/η]. An apparent activation energy for crosslinking of xanthan was calculated as Ea = 42 kJ/mol and Ea = 108 kJ/mol for Cr and Al ions, respectively. The fractal dimensionality of xanthan-Cr at the sol-gel transition was estimated as 1·3 applying the Chambon-Winter criterion for gelation, thus indicating that this gelation criterion is applicable also to stiff-chain polysaccharides such as xanthan. |