Protracted Crossover to Reptation Dynamics: A Field Cycling¹H NMR Study Including Extremely Low Frequencies

Abstract

The segmental dynamics of 1,4-polybutadiene is investigated by means of electronic field cycling 1H NMR. The frequency dependence (dispersion) of the spin–lattice relaxation time is probed over a broad range of temperature (223–408 K), molecular mass (355 ≤ M (g/mol) ≤ 441 000), and frequency (200 Hz–30 MHz). The extremely low frequencies are accessed by employing a home-built compensation for earth and stray fields extending prior reports about 2 decades to lower frequencies. Applying frequency–temperature superposition yields master curves over 10 decades in frequency (or time), and after Fourier transform the full dipolar correlation function is traced over up to 8 decades in amplitude. Several relaxation regimes can be identified, and their power-law exponents are compared to the predictions of the Doi–Edwards tube-reptation model, namely the free Rouse (I) and the constrained Rouse regime (II). Whereas the predicted value of the power-law exponent of regime II is 0.25, we find that it depends on M and levels off at 0.32 for very high M = 441 000 ≈ 220Me (Me: entanglement molecular mass). This is in good agreement with recent results from double quantum 1H NMR and indicates that the actual onset of full reptation dynamics is strongly protracted.