Aspects of the glass transition behaviour of mixtures of carbohydrates of low molecular weight.

The glass transition temperature (Tg) values for carbohydrates alone and in binary mixtures have been determined using differential scanning calorimetry. The Tg of the carbohydrate depends strongly on molecular weight and less on structure. The Tg of the binary mixtures was dependent on composition and, in most instances, was linear with respect to mole fraction. The effect of water on depressing the Tg of the carbohydrates and their binary mixtures was also evaluated. The observed behaviour was compared with that predicted from a thermodynamic approach.

Effect of water as a diluent on the glass transition behaviour of malto-oligosaccharides, amylose and amylopectin.

The glass transition behaviour of amorphous malto-oligomers from dimer to hexamer was investigated as a function of diluent (water) concentration using differential scanning calorimetry. The glass transition temperatures of the pure compounds ranged from 364 K for maltose to 448 K for maltohexaose. At low diluent concentrations the addition of water strongly depressed Tg. From the measurement of Tg and the heat capacity increment, delta Cp, of the transition for the pure compounds it was possible to predict the Tg of the malto-oligomer/water mixtures using a thermodynamic approach developed by Couchman. From the measurements on the malto-oligomers it was possible to obtain, by extrapolation, the high DP limits of delta Cp and Tg, which are appropriate to amylose and amylopectin. The predicted variation of Tg with diluent concentration for these materials was compared with the experimentally observed behaviour.

Aqueous dissolution of crystalline and amorphous amylose-alcohol complexes.

Complexes of amylose, the linear starch polysaccharide, with linear alcohols having chain lengths varying from 4 to 8 carbon atoms, were prepared. Either crystalline or amorphous complexes could be formed depending on preparation conditions. Crystalline complexes gave sharp X-ray diffraction patterns, characteristic of the VH form of amylose, whereas no observable pattern was obtained from the amorphous form. Thermal dissociation of the complexes occurred at increasing temperatures with increasing alcohol chain length. Crystalline complexes dissociated at temperatures approximately 23 degrees C higher than their amorphous counterparts and the enthalpy of dissociation was also greater for the crystalline samples. Enthalpy values were independent of alcohol chain length. Differences in thermal behaviour of the two types of complex may be described in terms of the polymer crystal lattice energy and may explain the variability of reported results for complex dissociation in the literature.