화학공학소재연구정보센터
Macromolecules, Vol.32, No.5, 1519-1527, 1999
Galactomannan gelation: A thermal and rheological investigation analyzed using the cascade model
High-temperature water soluble fractions of locust bean gum with average galactose contents of 15.2% and 16% w/w displayed conventional gelling behavior. Gel properties were dependent on galactose content, gelling temperature and concentration. The gels appeared elastic, failed at up to 150% strain, and exhibited true gellike character with long-lived cross-links. Rheological meltdown occurred over a broad temperature range, and the gels melted at temperatures between 100 and 110 degrees C. Cascade analysis of the storage modulus vs concentration data gave critical gelling concentrations, C-o = 0.14-0.24% w/w after 3 months gelation, but this analysis was unable to uniquely determine the number of potential cross-linking forming sites per molecule, i.e., the functionality, f. A value of f = 5, as well as average values of the standard molar enthalpy, Delta H degrees = -99.6 kJ/mol and standard molar entropy, Delta S degrees = -0.201 kJ/(mol K), for cross-link formation, was subsequently determined through an extension of the cascade formalism to describe modulus vs temperature meltdown data. That these values did not reflect equilibrium melting was shown by a detailed comparison of the analyses of concentration and temperature dependencies of the storage modulus using the cascade model and also by an increase in the number and length of cross-links after 8 months gelation time and by rheological annealing at slower heating rates. An attempt by simulation to assess errors introduced through the assumption of equilibrium gel melting indicated that the true functionality, f, was closer to 20 and that the idealized critical gelling concentrations (were the gels able to reach equilibrium) would be much smaller than the 0.14-0.24% w/w values obtained after 3 months. The simulation also showed that the real values of Delta H degrees and Delta S degrees were likely to be close to the estimates obtained using the equilibrium theory and nonequilibrium data obtained after 3 months.