Abstract

Despite decades of studies on the grand problem of the glass transition the question of well-defined universal patterns, including the key problem of the previtreous behavior of the primary (structural) relaxation time, remains elusive. This report shows the universal previtreous behavior of the apparent fragility, i.e. the steepness index mP (T > Tg) = d log10τ(T)/d( Tg/T). It is evidenced that mP(T) = 1(T − T*), for T → Tg and T*= Tg − Δ T*. Basing on this finding, the new 3-parameter dependence for portraying the previtreous behavior of the primary relaxation time has been derived: τ(T) = CΩ((T − T*)/T)−Ω × [exp((T − T*)/T)]Ω. The universality of obtained relations is evidenced for glass formers belonging to low molecular weight liquids, polymers (melt and solid), plastic crystals, liquid crystals, resins and relaxors. They exhibit clear preferences either for the VFT or for the critical-like descriptions, if recalled already used modeling. The novel relation can obey even above the dynamic crossover temperature, with the power exponent Ω ranging between ~17 (liquid crystals) to ~57 (glycerol), what may indicate the impact of symmetry on the previtreous effect. Finally, the emerging similarity to the behavior in the isotropic phase of nematic liquid crystals is recalled.

Highlights

  • The glass transition has remained the grand challenge of solid state physics and material engineering since decades

  • They were carried out for supercooled system ranging from low molecular weight liquids[54], polymers[55], resin (EPON 828: diglycyl ether of bisphenol-A)[56], liquid crystals (5CB: pentylcyanobiphenyl)57, 8*OCB58, disordered orientational crystals (ODIC, plastic crystals: the mixture of neopentyl alcohol (NPA) and neopentylglycol (NPG))[59] and the relaxor glass former in a hybrid system (30% volume fraction of 2 μm BaTiO3 microparticles in PVDF)[55]

  • The careful degassing of samples and the proper design of the measurement capacitor enabled the supercooling in the nematic phase down to the glass transition liquid crystals (LC) glassformers57. 8*OCB can be supercooled to Tg in the isotropic phase[58]

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Summary

Introduction

The glass transition has remained the grand challenge of solid state physics and material engineering since decades. The common key feature is the super-Arrhenius (SA) evolution of the primary (structural) relaxation time τ(T), viscosity η(T), ..8,9: τ(T ). Where T > Tg, Tg means the glass temperature; Ea(T) denotes the apparent activation energy: for Ea(T) = Ea = const the basic Arrhenius dependence is obtained. Angell et al.[10,11] proposed normalized plots log10η(T) and log10τ(T) versus Tg/T

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