From Simple Liquid to Polymer Melt. Glassy and Polymer Dynamics Studied by Fast Field Cycling NMR Relaxometry: Low and High Molecular Weight Limit

Abstract

Fast field cycling (FFC) NMR is applied to study the dispersion of the 1H spin−lattice relaxation in the low molecular weight glass-formers o-terphenyl, tristyrene, and oligomeric polybutadiene (PB, with M/gmol−1 = 355 and 466) over a broad temperature range (203−401 K). Differing from previous FFC NMR works, we analyze the relaxation data in the susceptibility form ω/T1(ω), and applying frequency−temperature superposition, master spectra are obtained covering up to 8 decades in frequency. In all cases solely the glassy dynamics (α-process) determines the relaxation behavior, and the Rouse unit is estimated to MR ≅ 500 g/mol. The time constant τα(T) in the range 10−11−10−6 s is extracted, which agrees well with those measured at the same time by dielectric spectroscopy. For the high molecular weight PB (M/gmol−1 = 56 500, 87 000, 314 000, and 817 000) pronounced polymer effects are observed at low frequencies (ωτα ≪ 1) which are isolated from the total spectrum by subtracting the “glass spectrum” as obtai...