Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

Abstract:

:It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

authors

Mallamace F,Branca C,Corsaro C,Leone N,Spooren J,Chen SH,Stanley HE

doi

10.1073/pnas.1015340107

subject

Has Abstract

pub_date

2010-12-28 00:00:00

pages

22457-62

issue

52

eissn

0027-8424

issn

1091-6490

pii

1015340107

journal_volume

107

pub_type

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