Kinetic criteria of glass-formation, pressure dependence of the glass-transition temperature, and the Prigogine–Defay ratioстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 12 июля 2019 г.
Аннотация:An analysis of some current topics of discussion in the theoretical modeling of the glass transition and of glass
properties is given. In the first part, a general model-independent kinetic criterion of glass-formation is formulated.
Its interrelation with other attempts of formulation of such criteria is discussed and some consequences not
studied so far in detail are analyzed. It is shown that the value of the glass transition temperature depends not
only on system properties and rates of change of external control parameters but, as a rule, also on the property
of the system measured for its specification. In addition, systems described by several structural orderparameters
may exhibit multiple glass transitions. The respective glass transition temperatures are shown to
depend on the spectrumof relaxation times of the respective structural order-parameter and the degree of deviation
of the systemfromthe thermodynamic equilibriumstate. Employing mentioned kinetic criteria, further on
general equations for the pressure dependence of the glass transition temperature and the value of the viscosity
at the glass transition temperature in dependence on cooling rate are formulated. In the second part, existing
different approaches to the theoretical determination of the Prigogine–Defay (PD) ratio in glass transition are
critically reviewed. As shown, following the kinetic approach to the determination of the glass transition temperature
Tg, the analysis of the pressure dependence of Tg does not lead to any generally valid predictions for the
value of the PD-ratio. It is demonstrated further that some recent attempts to question it do not affect the
basic result of earlier analysis (J. W. P. Schmelzer and I. Gutzow, J. Chem. Phys. 125, 184511/1-11 (2006))
concerning the possibility to predict theoretically values of the PD-ratio larger than onewhen only one structural
order-parameter is employed to describe kinetic freeze-in at glass transition.