Thermochimica Acta, Vol.284, No.1, 191-212, 1996
Observation of Multiple Glass Transitions in the System Water/1,3-Butanediol - Effect on Ice Crystallization
A thermal analysis approach is presented to analyze the interaction between ice nucleation and glass transition. Double glass transitions are observed using calorimetry for the system 1,3-butanediol-water for concentrations less than 30% mole/mole in water as previously shown for 1,2-propanediol. Annealing experiments above the main glass transition temperatures reveal a third endothermic transition identified as a glass transition peak. The thermal range of this third glass transition is - 107 to - 97 degrees C for 15% mole/mole 1,3-butanediol in water. For this concentration, ice crystallization was suppressed during cooling at 10 degrees C min(1) but still occurred during the subsequent warming. Analysis of the devitrification temperature and of the amount of ice during warming show that annealing conditions do increase the ice nuclei density and do modify the crystal growth kinetics either by dissociating cubic and hexagonal ice nucleus formation or by structurally changing the crystal growth characteristics. The total amount of ice crystallizing during warming remains constant for annealings below - 95 degrees C for several hours. The third glass transition was shown to be independent of the ice nucleus density during annealing. A decrease in the size of both first glass transitions, mostly of the first glass transition, is observed as the magnitude of the third glass transition increases. This relates the existence of the third glass transition to the existence of the first glass transition. The structural relaxation associated with the third glass transition is shown not to affect the ice crystallization kinetics.
Keywords:AQUEOUS-SOLUTIONS;HOMOGENEOUS NUCLEATION;4 CARBONS;VITRIFICATION;GROWTH;CRYOPRESERVATION;DEVITRIFICATION;POLYALCOHOLS;CRYSTALS;LIQUIDS