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  • Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

The Journal of chemical physics (2015-05-17)
Satya N Tripathy, Zaneta Wojnarowska, Justyna Knapik, Hideaki Shirota, Ranjit Biswas, Marian Paluch
RÉSUMÉ

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10(-1)-10(6) Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

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Sodium thiocyanate, ≥99.99% trace metals basis