Dynamics of asymmetric binary glass formers. II. Results from nuclear magnetic resonance spectroscopy

Abstract

Various (2)H and (31)P nuclear magnetic resonance (NMR) spectroscopy techniques are applied to probe the component dynamics of the binary glass former tripropyl phosphate (TPP)/polystyrene-d3 (PS) over the full concentration range. The results are quantitatively compared to those of a dielectric spectroscopy (DS) study on the same system previously published [R. Kahlau, D. Bock, B. Schmidtke, and E. A. Rössler, J. Chem. Phys. 140, 044509 (2014)]. While the PS dynamics does not significantly change in the mixtures compared to that of neat PS, two fractions of TPP molecules are identified, one joining the glass transition of PS in the mixture (α1-process), the second reorienting isotropically (α2-process) even in the rigid matrix of PS, although at low concentration resembling a secondary process regarding its manifestation in the DS spectra. Pronounced dynamical heterogeneities are found for the TPP α2-process, showing up in extremely stretched, quasi-logarithmic stimulated echo decays. While the time window of NMR is insufficient for recording the full correlation functions, DS results, covering a larger dynamical range, provide a satisfactory interpolation of the NMR data. Two-dimensional (31)P NMR spectra prove exchange within the broadly distributed α2-process. As demonstrated by (2)H NMR, the PS matrix reflects the faster α2-process of TPP by performing a spatially highly hindered motion on the same timescale.