Viscoelastic Reversibility of Carrageenan Hydrogels under Large Amplitude Oscillatory Shear: Hybrid Carrageenans...

The viscoelastic response of carrageenan hydrogels to large amplitude oscillatory shear (LAOS) has not received much attention in the literature in spite of its relevance in industrial application. A set of hybrid carrageenans with differing chemical compositions are gelled in the presence of KCl or NaCl, and their nonlinear viscoelastic responses are systematically compared with mixtures of kappa- and iota-carrageenans of equivalent kappa-carrageenan contents. Two categories of LAOS response are identified: strain softening and strain hardening gels. Strain softening gels show LAOS non-reversibility: when entering the nonlinear viscoelastic regime, the shear storage modulus G' decreases with increasing strain, and never recovers its linear value G₀ after successive LAOS sweeps. In contrast to this, strain hardening carrageenan gels show a certain amount of LAOS reversibility: when entering the nonlinear regime, G' increases with strain and shows a maximum at strain γ_H. For strains applied below γ_H, G₀ shows good reversibility and the strain hardening behavior is maintained. For strains larger than γ_H, G₀ decreases significantly indicating an irreversible structural change in the elastic network. Strain hardening and elastic recovery after LAOS prevail for hybrid carrageenan and iota-carrageenan gels, but are only achieved when blends are gelled in NaCl, suggesting a phase separated structure with a certain degree of co-aggregated interface for mixed gels.