Influence of shear deformation on the formation of dynamic structure in protic ionic liquids. Representation of the temperature dependence of viscosity within the framework of Angell’s fragility concept

Abstract

The rheological properties of a liquid containing two types of basic centers and hydroxyl groups (BGE-Im), as well as protic ionic liquids (ILs) derived from it, were studied in a wide range of shear rates (γ̇) (10−6–103 s−1) at various temperatures from 10 to 50 °C. Viscosity (η) of the BGE-Im does not depend on the scanning direction of shear stress (σ), i.e. this compound behaves like a Newtonian fluid over the entire range of σ. The dependence log η (1/T) of BGE-Im in Arrhenius coordinates is linear. Protonation of basic centers of BGE-Im leads to a strong increase in the viscosity of ILs obtained on its basis, and the temperature dependence of the viscosity of these ILs is described by the Vogel–Fulcher–Tammann (VFT) equation. It has been established that in the region of low shear rates, the viscosity of the ILs increases with decreasing shear rate, which leads to the appearance of a yield stress (σY). This indicates the formation of a fluctuation rheopectic structure in the ILs. In this sense, ILs are heterogeneous systems and their behavior is similar to that of highly concentrated suspensions and emulsions. For the first time, a quantitative comparison between the parameters of the VFT equation, the fragility (according to Angell’s model) of ILs, the relative coordination number of ILs molecules and the rheological yield stress characterizing the shear-induced fluctuation rheopectic structure of ILs has been made and the relationship between these characteristics has been shown.