Viscoelastic properties of ultra-high viscosity alginates

Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHV_N, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHV_T, containing 22% M and 78% G). The viscoelastic behavior of the aqueous solutions of these alginates was determined in shear flow in terms of the shear stress σ₂₁, the first normal stress difference N₁, and the shear viscosity η in isotonic NaCl solutions (0.154 mol/L) at T = 298 K in dependence of the shear rate γ̇ for solutions of varying concentrations and molar masses (3-10 × 10⁵ g/mol, homologous series was prepared by ultrasonic degradation). Data obtained in small-amplitude oscillatory shear (SAOS) experiments obey the Cox-Merz rule. For comparison, a commercial alginate with intermediate chemical composition was additionally characterized. Particulate substances which are omnipresent in most alginates influenced the determination of the material functions at low shear rates. We have calculated structure-property relationships for the prediction of the viscosity yield, e. g., η-M_w-c-γ̇ for the Newtonian and non-Newtonian region. For the highest molar masses and concentrations, the elasticity yield in terms of N₁ could be determined. In addition, the extensional flow behavior of the alginates was measured using capillary breakup extensional rheometry. The results demonstrate that even samples with the same average molar mass but different molar mass distributions can be differentiated in contrast to shear flow or SAOS experiments.