The susceptibility spectra of ten molecular glass formers are completely interpolated by an extension of the generalized gamma distribution of correlation times. The data cover at least 15 decades in frequency and the interpolation includes both alpha peak and excess wing. It is shown that the line shape parameters and the time constant of the alpha relaxation are related to each other. Master curves are identified by a scaling procedure that involves only three parameters, namely, the glass transition temperature T(g), the fragility m, and the excess wing exponent at T(g). This holds independent of whether a further secondary relaxation peak is present or not. Above a crossover temperature T(x) this unique evolution of the line shape parameters breaks down, and a crossover to a simple peak susceptibility without excess wing is observed. Here, the frequency-temperature superposition principle holds in good approximation up to temperatures well above the melting point. It turns out that the crossover coincides with the temperature at which the low-temperature Vogel-Fulcher law starts to fail upon heating. Thus, the so-called Stickel temperature gets a more physical meaning as it marks a qualitative change in the evolution of the susceptibility spectra of glass formers. Moreover, the interrelation of the line shape parameters can explain why the "Nagel scaling" works in some approximation. Our study demonstrates that the excess wing in molecular glass formers is a secondary relaxation, which is linked to the alpha process in a unique way.
We investigated binary low-molecular-weight glass formers as model systems for mixtures of small and large
molecules. Tricresyl phosphate (TCP) in oligomeric styrenes (OS), benzene in OS and polystyrene (PS), and
benzene in TCP were studied by applying dielectric spectroscopy as well as 1H, 2H, and 31P NMR spectroscopy.
Temperatures above and below the glass-transition temperature (T
G) are covered. The dielectric loss of the
small component appears broader the higher the molecular ratio M/m is, and the lower the TCP concentration
and the lower the temperature are chosen. Close to T
G, extremely broad distributions of correlation times
G(log τ) result, which are similar to those reported in the cases of polymer−plasticizer systems, although for
our systems the motional heterogeneities are already established at similar M and m. By applying 1H and 2H
(1D and 2D) NMR on benzene in OS and PS, we can demonstrate that the large molecules basically behave
as in neat glass formers. However, the small molecules exhibit an isotropic reorientation also well below T
G,
and the dynamics is rather characterized by a random jump process than by rotational diffusion, the latter
being found in neat systems. Furthermore, we can prove that within G(log τ), exchange processes take place,
even below T
G, which essentially occur on the same time scale as reorientation.
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