Relaxation and diffusion of an ionic plasticizer in amorphous poly(vinylpyrrolidone)

Abstract

The present work focuses on the dynamics of the ionic constituents of 1-propyl-3-methyl-imidazolium-bis-(trifluormethylsulfonyl)-imide (PT), a paradigmatic ionic liquid, as an additive in poly(vinylpyrrolidone) (PVP). Hence, the resulting product can be regarded as a polymer electrolyte as well as an amorphous dispersion. Leveraging dielectric spectroscopy and oscillatory shear rheology, complemented by differential scanning calorimetry, the spectral shapes and the relaxation maps of the supercooled PVP-PT mixtures are accessed in their full compositional range. The study also presents dielectric and shear responses of neat PVP with a molecular weight of 2500 g mol⁻¹. We discuss the plasticizing role of the PT additive and the decoupling between ionic dynamics and segmental relaxation in these mixtures. The extracted relaxation times, steady-state viscosities, and conductivities are employed to estimate the translational diffusivities of the ionic penetrants by means of the Stokes–Einstein, Nernst–Einstein, and Almond–West relations. While some of the estimated diffusivities agree with each other, some do not, pointing to the importance of the chosen hydrodynamic approximations and the type of response considered for the analysis. The present extensive dielectric, rheological, and calorimetric study enables a deeper understanding of relaxation and transport of ionic ingredients in polymers, particularly in the slow-dynamics regime which is difficult to access experimentally by direct-diffusivity probes.