Citation
E. Miyoshi et al., EFFECTS OF SALTS ON THE GEL-SOL TRANSITION OF GELLAN GUM BY DIFFERENTIAL SCANNING CALORIMETRY AND THERMAL SCANNING RHEOLOGY, Thermochimica acta, 267, 1995, pp. 269-287
Abstract
The rheological and thermal properties of sodium form gellan gum solut
ions with and without sodium chloride, potassium chloride, calcium chl
oride and magnesium chloride were studied by dynamic viscoelastic meas
urement and differential scanning calorimetry, Temperature dependence
of the loss modulus for gellan gum solutions of lower concentrations w
ithout salt showed a one step-like change at a certain temperature, ho
wever that for concentrated gellan gum solutions (>2.0%) showed two st
ep-like changes. The higher temperature process T-hc may be attributed
to the helix-coil transition and found in between the exothermic and
endothermic peak temperatures T-s and T-m observed in cooling and heat
ing DSC curves, while the lower temperature process T-sg may be attrib
uted to the sol-gel transition. Temperature dependence for gellan gum
solutions of higher concentrations (>3.2%) showed a large hysteresis,
moreover, the temperature at which the loss shear modulus G '' showed
the second step decrease shifted to higher temperatures with increasin
g concentration of gellan gum. The cooling or heating DSC curves for g
ellan gum solutions of lower concentrations showed a single exothermic
or endothermic peak, and both exothermic peak temperature T-m and end
othermic peak temperature T-m shifted to higher temperatures, and both
exothermic and endothermic enthalpies increased with increasing conce
ntration of gellan gum. However, for a gellan gum solution of a concen
tration higher than 3.2%, the endothermic peak in the heating DSC curv
e split into two peaks, while the cooling curve showed only one endoth
ermic peak. The lower temperature endothermic peak in the heating DSC
curve corresponds with the first step decrease of G '' in the heating
process of rheological measurement, and the higher temperature endothe
rmic peak corresponds with the second step decrease of G ''. The visco
elastic change of gellan gum solutions was more remarkable by the addi
tion of K+ than Na+, and by Ca2+ than by Mg2+. The viscoelastic behavi
or of gellan gum solutions was influenced much more strongly by divale
nt cations than by monovalent cations. DSC cooling curves of gellan gu
m solutions showed a single exothermic peak shifting to progressively
higher temperatures with increasing concentration of monovalent cation
s. At low concentration of monovalent cations, the DSC heating curves
showed a single endothermic peak, however, with more progressive addit
ion of salt, the endothermic peak gradually developed bimodal characte
r and eventually split into multiple peaks. With increasing concentrat
ion of divalent cations, the exothermic and endothermic enthalpies est
imated for a main peak increased up to a certain concentration and the
n decreased. Moreover, the endothermic peaks in the presence of suffic
ient salts were too broad to be resolved from the baseline, and many o
ther peaks were observed at higher temperatures. Gellan gum solutions
with sufficient divalent cations form firm gels on cooling to below th
e setting temperature, and then it was difficult to remelt them, which
was quite different from the behavior of thermoreversible gels formed
in the presence of monovalent cations.