Calorimetric, thermomechanical, and rheological characterizations of bulk glass-forming Pd40Ni40P20

Calorimetric, thermomechanical, and rheological properties of undercooled liquid Pd40Ni40P20 were determined within a wide temperature range above the glass transition. The concept of the limiting fictive temperature was applied to the entire set of measurements to compare the different properties adequately. It was found that an equilibrium state of a sample that is defined by its calorimetric glass temperature corresponds to a similar equilibrium state for the specific volume and for the shear viscosity as well. The Kauzmann temperature as one of the most important material characteristics concerning the glass transition could be determined with high acuracy leading to the evaluation of the free volume persistent in the samples. Viscosity values of the liquid extending over a range of about nine orders in magnitude could be described best by the free volume theory evaluated by Cohen and Grest, provided that expertimentally obtained parameters were used for the calculation. The comparison between nonequilibrium measurements at isochronous heating and model calculations in the framework of bimolecular reaction kinetics shows that good agreement can be achieved using thermodynamic parameters that have been obtained from equilibrium measurements. However, systematic deviations indicate also the limitations of the model that are related to the intrinsic dynamic heterogeneity of the vitreous state