Combined description of pressure–volume–temperature and dielectric relaxation of several polymeric and low-molecular-weight organic glass-formers using SL-TS2 approach

Abstract

We apply our recently-developed mean-field “SL-TS2” (two-state Sanchez–Lacombe) model to simultaneously describe dielectric α-relaxation time, τ_α, and pressure–volume–temperature (PVT) data in four polymers (polystyrene, poly(methylmethacrylate), poly(vinyl acetate) and poly(cyclohexane methyl acrylate)) and four organic molecular glass formers (ortho-terphenyl, glycerol, PCB-62, and PDE). Previously, it has been shown that for all eight materials, the Casalini–Roland thermodynamical scaling, τ_α = f(Tv^γ_sp) (where T is temperature and v_sp is specific volume) is satisfied (R. Casalini and C. M. Roland, Phys. Rev. E, 2004, 69(6), 62501). It has also been previously shown that the same scaling emerges naturally (for sufficiently low pressures) within the “SL-TS2” framework (V. V. Ginzburg, Soft Matter, 2021, 17, 9094–9106). Here, we fit the ambient pressure curves for the relaxation time and the specific volume as functions of temperature for the eight materials and observe a good agreement between theory and experiment. We then use the Casalini–Roland scaling to convert those results into “master curves”, thus enabling predictions of relaxation times and specific volumes at elevated pressures. The proposed approach can be used to describe other glass-forming materials, both low-molecular-weight and polymeric.