Temperature Dependence of Intermediate-Range Orders Through the Glass Transition and Their Self-Organization

Hiroshi      Kobayashi

Abstract

The relaxation time-temperature relationship is analyzed by extending the Adam-Gibbss theory to the range below the glass transition temperature (Tg). The entropy change of Intermediate-Range Orders (IROs) is discussed on the basis of Prigogines theory. The glass transition is a non-equilibrium phase transition from a Vogel-Fulcher-Tamman state to an Arrhenius state through fluctuations at Tg, and a microscopic feature of the glass transition is the self-organization of IROs. The time dependence of the configurational entropy of glass is zero, but that of its vibrational entropy shows a constant decrease with the smallest change, maintaining an isostructural state. These results indicate that the volume of glass decreases at a constant time rate through spontaneous aging at a constant temperature. The nanometer-size of IROs in glass determines the residual entropy. The glass transition is a nano-emergence through the abrupt decrease in fluctuations in the supercooled liquid state, which is caused by the sudden strengthener of correlations between IROs at Tg. Finally, it is proposed that glass is the 4th state after gas, liquid and crystal and the time symmetry in glass is spontaneously violated. These findings are extremely useful for understanding glass and nanomaterial, because the size of IROs in the glass state is a few nanometers.

Keywords: Entropy, glass transition, intermediate-range order, nano-emergence, nanomaterial, non-equilibrium, selforganization, supercooled liquid, atomic force microscopy, configurational entropy, heterogeneity, reflection spectra, shear, vibrational heat capacity