Rheology of concentrated isotropic and anisotropic xanthan solutions: 3. Temperature dependence

The oscillatory rheology of one rodlike and one semiflexible xanthan sample has been investigated as a function of temperature in the range of xanthan concentrations where the polymer forms a lyotropic liquid crystalline phase in aqueous NaCl solutions. Readily observed changes in the rheological observables at temperatures corresponding to phase boundaries permit construction of the biphasic chimney region of the temperature-composition phase diagram. The chimney region leans toward larger values of the polymer concentration with increasing temperature, presumably as a consequence of a reduction in the effective axial ratio of the helical polymer with increasing temperature. The results permit construction of plots of the rheological observables as a function of polymer concentration at temperatures T in the range 20 less than or equal to T less than or equal to 90 degreesC. Characteristic features of these curves observed at room temperature are preserved it higher temperatures, provided the xanthan double helix remains intact, The temperature dependence of the viscosity of isotropic xanthan solutions can be described with the Arrhenius law. For anisotropic solutions the viscosity increases with T at the higher end of the experimental temperature range, presumably because higher temperatures reduce the order parameter of the liquid crystalline phase with a concomitant increase in viscosity. At low NaCl concentration, and low polymer concentration, the xanthan helix order-disorder transition occurs at temperatures T-m below 90 degreesC. At temperatures above T-m the rheological observables reveal the onset of network formation involving xanthan chains released from the ordered helical structure. When these systems are cooled back below T-m, extensive network formation develops with large increases in viscosity and in the storage and loss moduli.