The phenomenology of metastable liquids and the glass transition

The Third Principle of thermodynamics and the zero-point entropy of glasses: History and new developments

“…In a series of more recent publications Gutzow, Schmelzer et al [35,42,45], developed from the non-linear formulation of Eq. (23) in a generic way dependences, in which, as first considered by Prigogine [44], a function of the activation energy, U, of the time of molecular relaxation, s, on the deviation from equilibrium, i.e.…”

“…Thus as pointed out in [22,23,35] T g is to be considered as a particular form of a kinetic degeneration temperature, h Tg , where C config p ðT; nÞ degenerates to zero and only C phon p ðTÞ remains as the phononic specific heat of glass.…”

“…In a more convenient approach [22,23,35,36] n can be introduced [17] in such a way that the affinity A(T, n) of the process investigated is a linear function of the deviation from equilibrium of the parameter n, which as we assume, describes a in generalized way the structure of the system AðT; nÞ ¼ G ð2Þ ðn À n eq Þ: ð13Þ…”

Affinity and its derivatives in the glass transition process

“…17 Among these recent works, Gutzow, Schmelzer, and co-workers have brought new aspects to the field. [18][19][20][21][22][23][24] Using the so-called lattice-hole theory of liquids, and an evolution equation for the order parameter as a function of temperature, they investigated the process of vitrification and structural recovery following defined temperature protocols. 18,19,23,24 Among other points, a new expression for the Prigogine-Defay ratio and a thermodynamic definition of the fictive temperature was provided.…”

Structural order parameters, the Prigogine–Defay ratio and the behavior of the entropy in vitrification

“…(iii) The third law of thermodynamics in its conventional formulation assigned to Planck [15,16] is not fulfilled, since glasses are frozen-in non-equilibrium systems characterized by excess values of the thermodynamic potentials and, in particular, the entropy. For this reason, the entropy of glasses does not follow the third law of thermodynamics in the conventional form ([1], a more detailed discussion of the limits of applicability of the third law of thermodynamics to glasses is given in [17][18][19] and in [32] of the present volume).…”