title: Deducting the temperature dependence of the structural relaxation time in equilibrium far below the nominal Tg by aging the decoupled conductivity relaxation to equilibrium.
abstract: Using broadband dielectric spectroscopy we investigate the changes in the conductivity relaxation times τσ observed during the physical aging of the protic ionic conductor carvedilol dihydrogen phosphate (CP). Due to the large decoupling of ion diffusion from host molecule reorientation, the ion conductivity relaxation time τσ(Tage,tage) can be directly measured at temperatures Tage below Tg for exceedingly long aging times tage till τσ(Tage,tage) has reached the equilibrium value τσ(eq)(Tage). The dependence of τσ(Tage,tage) on tage is well described by the stretched exponential function, τσ(Tage, tage) = Aexp[-((tage)/(τage(Tage)))(β)] + τσ(eq)(Tage), where β is a constant and τage(Tage) can be taken as the structural α-relaxation time of the equilibrium liquid at T = Tage. The value of τσ(eq)(Tage) obtained after 63 days long annealing of CP, deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHσ) dependence of τσ(T) determined from data taken above Tg and extrapolated down to Tage. Concurrently, τage(Tage) also deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHα) dependence. The results help to answer the longstanding question of whether the VFTH dependence of τσ(T) as well as the structural α-relaxation time τα(T) holds or not in the equilibrium liquid state far below Tg.
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: Z
authors.initials: Z
authors.lastname: Wojnarowska
authors.affiliation: Dipartimento di Fisica, Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa, Italy.
authors.forename: K L
authors.initials: KL
authors.lastname: Ngai
authors.affiliation: Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice, Poland.
authors.forename: M
authors.initials: M
authors.lastname: Paluch