In search of invariants for viscous liquids in the density scaling regime: investigations of dynamic and thermodynamic moduli

Abstract

In this paper, we report the nontrivial results of our investigations of dynamic and thermodynamic moduli in search of invariants for viscous liquids in the density scaling regime by using selected supercooled van der Waals liquids as representative materials. Previously, the dynamic modulus M_p–T (defined in the pressure–temperature representation by the ratio of isobaric activation energy and activation volume) as well as the ratio B_T/M_p–T (where B_T is the thermodynamic modulus defined as the inverse isothermal compressibility) have been suggested as some kinds of material constants. We have established that they are not valid in the explored wide range of temperatures T over a dozen decades of structural relaxation times τ. The temperature dependences of M_p–T and B_T/M_p–T have been elucidated by comparison with the well-known measure of the relative contribution of temperature and density fluctuations to molecular dynamics near the glass transition, i.e., the ratio of isochoric and isobaric activation energies. Then, we have implemented an idea to transform the definition of the dynamic modulus M_p–T from the p–T representation to the V–T one. This idea relied on the disentanglement of combined temperature and density fluctuations involved in isobaric parameters and has resulted in finding an invariant for viscous liquids in the density scaling regime, which is the ratio of thermodynamic and dynamic moduli, B_T/M_V–T. In this way, we have constituted a characteristic of thermodynamics and molecular dynamics, which remains unchanged in the supercooled liquid state for a given material, the molecular dynamics of which obeys the power density scaling law.