0000000000624101
AUTHOR
A. Döß
From strong to fragile glass formers: secondary relaxation in polyalcohols.
We have studied details of the molecular origin of slow secondary relaxation near T(g) in a series of neat polyalcohols by means of dielectric spectroscopy and (2)H NMR. From glycerol to threitol, xylitol, and sorbitol the appearance of the secondary relaxation changes gradually from a wing-type scenario to a pronounced beta peak. It is found that in sorbitol the dynamics of the whole molecule contributes equally to the beta process, while in glycerol the hydrogen bond forming OH groups remain rather rigid compared to the hydrogens bonded to the carbon skeleton.
Nuclear Spin Relaxation in Viscous Liquids: Relaxation Stretching of Single-Particle Probes
Spin-lattice relaxation rates R1(ω,T), probed via high-field and field-cycling nuclear magnetic resonance (NMR), are used to test the validity of frequency-temperature superposition (FTS) for the reorientation dynamics in viscous liquids. For several liquids, FTS is found to apply so that master curves can be generated. The susceptibility spectra are highly similar to those obtained from depolarized light scattering (DLS) and reveal an excess wing. Where FTS works, two approaches are suggested to access the susceptibility: (i) a plot of deuteron R1(T) vs the spin-spin relaxation rate R2(T) and (ii) a plot of R1(T) vs an independently measured reference time τref(T). Using single-frequency s…
Spatial heterogeneity in glassy polystyrene detected by deuteron NMR relaxation
Using deuteron NMR, the dynamics of supercooled polystyrene-d 3 was investigated near the calorimetric glass transition. At these temperatures non-exponential spin lattice relaxation is found, indicating the presence of spatial heterogeneity. With increasing temperature, structural relaxation becomes fast enough to average efficiently over different spatial environments, leading to exponential magnetization decays. A qualitative comparison with toluene as a representative of a low molecular weight glass former is carried out. Indications are found that in polystyrene the observed averaging process is more effective at T g than it is in toluene.