Identification of dielectric and structural relaxations in glass-forming secondary amides

Dielectric relaxation dynamics of secondary amides is explored in their supercooled state near the glass transition temperature Tg by investigating N -ethylacetamide and its mixtures with N -methylformamide. All the samples are found to exhibit giant dielectric permittivities, reaching over 500 in N -methylformamide-rich mixtures around Tg. For both the neat and binary systems, the predominant relaxation peak is of the Debye-type throughout the viscous regime, which is an unexpected feature for a glass former with intermediate fragility. The present results combined with the earlier reported high-temperature data reveal that the dielectric strength Δ εD of the Debye relaxation extrapolates to zero at frequencies of 1010 - 1011 Hz, which is about two orders of magnitude lower than the phonon frequency limit typical of the structural relaxation. This Debye process is remarkably similar to the dielectric behavior of many monohydroxy alcohols, which implies a common nature of purely exponential relaxation dynamics in these liquids. Based on the dielectric properties, we conclude that the Debye relaxation in the secondary amides is not a direct signature of the primary or α -relaxation, the latter being obscured at low temperatures due to the relatively low permittivity and close spectral proximity to the Debye peak. As in the case of monohydroxy alcohols, dielectric polarization and structure fluctuate on different time scales in secondary amides. The Kirkwood-Fröhlich correlation factors for Debye-type liquids are also discussed.