Field-Cycling Relaxometry as a Molecular Rheology Technique: Common Analysis of NMR, Shear Modulus and Dielectric Loss Data of Polymers vs Dendrimers

Abstract

Linear poly(propylene glycol) (PPG) as well as a poly(propyleneimine) (PPI) dendrimer with different molar masses (M) are investigated by field-cycling (FC) 1H NMR, shear rheology (G) and dielectric spectroscopy (DS). The results are compared in a reduced spectral density representation: the quantity R1(ωτα)/R1α(0), where R1(ωτα) is the master curve of the frequency dependent spin–lattice relaxation rate with τα denoting the local correlation time, is compared to the rescaled dynamic viscosity η′(ωτα)/η′α(0). The quantities R1α(0) and η′α(0), respectively, are the zero-frequency limits of a simple liquid reference system. Analogously, the dielectric loss data can be included in the methodological comparison. This representation allows quantifying the sensitivity of each method with respect to the polymer-specific relaxation contribution. Introducing a “cumulative mode ratio” Fi(M) for each technique i, which measures the zero-frequency plateau of the rescaled spectral density, characteristic power-law beh...