Gel—sol transition in gellan gum solutions. II. DSC studies on the effects of salts

Abstract

The thermal properties of sodium form gellan gum solutions with and without sodium chloride, potassium chloride, calcium chloride and magnesium chloride were studied by differential scanning calorimetry (DSC). The DSC cooling or heating curves for 1% gellan gum solutions without salt showed a single exothermic or endothermic peak at ~30°C. DSC cooling curves showed a single exothermic peak, with the setting temperature ( Ts) shifting to progressively higher temperatures with increasing concentration of the added NaCl or KCl. At low concentrations of NaCl or KCl, DSC heating curves showed a single endothermic peak; however with more addition of salt the endothermic peak gradually developed a bimodal character and eventually split into more than two distinct peaks. The onset of detectable splitting occurred at a high salt concentration which coincided with that at which elastic gels are formed at even a higher temperature as was observed by viscoelastic measurements. With a sufficient addition of monovalent cations the endothermic curve became again a single peak shifting to higher temperatures. In the presence of divalent cations, although Ts shifted to higher temperatures with increasing concentration of added CaCl 2 or MgCl 2, the melting temperature ( Tm) in heating DSC curves shifted to higher temperatures (up to a certain temperature) and then shifted to lower temperatures with increasing concentration of salt. With increasing concentration of CaCl 2 or MgCl 2, the exothermic and endothermic enthalpies estimated for a main peak increased up to a certain salt concentration and then decreased; however many other peaks were observed at higher temperatures. The endothermic peaks for gels with excessive divalent cations were too broad to be resolved from the baseline; in contrast the exothermic peaks were much sharper and readily recognized. In comparing thermal properties with rheological properties, gellan gum solutions with excessive divalent cations form firm gels on cooling to below the setting temperature, and then it was difficult to remelt them. This was quite different from the behaviour of thermoreversible gels formed in the presence of monovalent cations. It seems that the mechanism of gel formation in gellan gum with divalent cations is markedly different from that with monovalent cations.