Viscoelastic properties for kappa- and iota-carrageenan in aqueous NaI from the liquid-like to the solid-like behaviour

The dynamic mechanical behaviour of a series of concentrations of kappa-carrageenan (KC; 0.35-1.6% w/w) and iota-carrageenan (IC; 0. 2-1% w/w) in 0.2 M NaI has been investigated. The flow behaviour of KC within the concentration range 0.004-0.8% (w/v) was also described. The high intrinsic viscosity of KC in 0.2 M NaI (23.4 dl g(-1)) and the great increase in viscosity with increasing concentration, in comparison with linear flexible polysaccharides, is well consistent with the stiffness of KC helices in NaI. The variation of the 'zero-shear' specific viscosity of KC in 0.2 M NaI with the degree of space-occupancy (c[eta]) displays two critical concentrations at c* approximately 0.09% w/v (c*[eta] approximately 2) and c** approximately 0.4% w/v (c**[eta] approximately 10). Different viscoelastic behaviours were exhibited from the liquid-like to the solid-like depending upon the type of carrageenan. From the application of the time-temperature superposition, classical frequency-temperature master curves could be obtained for KC, but not for IC. Moreover, for KC, a concentration-frequency master curve could be constructed for the concentrations below 1.5%, indicating a 'solution-like' behaviour in this entire concentration range, although systems above 0.8% were visually gel-like. It is proposed that the rigidity of the KC helices is responsible for the slow relaxation rates of the gel-like samples. At higher concentrations (beyond 1.6%) a frequency-temperature superposition was no longer possible. In contrast to KC, IC behaved as a typical viscoelastic gel with a very weak frequency dependence of the storage modulus at all temperatures. This indicates the existence of associations beyond simple entanglements for IC. Creep experiments performed at higher carrageenan concentrations in 0.1 M NaI further corroborated the differences in the viscoelastic behaviour between KC and IC.