Monohydroxy alcohols (MAs) with methyl and hydroxyl side groups attached to the same carbon atom in the alkyl backbone can display very weak structural and supramolecular dielectric relaxation processes when probed in the regime of small electrical fields. This can render their separation and assignment difficult in the pure liquids. When mixing with bromoalkanes, a faint Debye-like process can be resolved dielectrically for 4-methyl-4-heptanol. To achieve a separation of structural and supramolecular processes in pure 4-methyl-4-heptanol and 3-methyl-3-heptanol, mechanical experiments are carried out in the linear-response regime as well as using medium-angle oscillatory shear amplitudes. It is demonstrated that first-order and third-order nonlinear mechanical effects allow for a clear identification of supramolecular viscoelastic modes even for alcohols in which they leave only a weak signature in the linear-response shear modulus. Additionally, the nonlinear rheological behavior of 2-ethyl-1-hexanol is studied, revealing that its linearly detected terminal mode does not coincide with that revealed beyond the linear-response regime. This finding contrasts with those for the other MAs studied in this work.

Medium-amplitude oscillatory shear experiments are employed to study the supramolecular relaxation modes in hydroxyl-terminated polydimethylsiloxane. For these associating melts, this allowed us to identify the nonlinear rheological signature of hydrogen-bond-mediated structures occurring in addition to those of the covalent chains. First-order and third-order nonlinearity parameters are determined for the supramolecular and chainlike modes to compare them with the predictions of an array of rheological models. Fingerprints of the two supramolecular modes can be recognized in the nonlinear response. By collecting third-order nonlinearity parameters 3 Q 0 for about 35 materials including polymer melts, polymer solutions, and other viscoelastic fluids, it is demonstrated that the maximum value of 3 Q 0 correlates with the magnitude of the shear modulus at the frequency at which this maximum occurs. The implications of this experimental finding are discussed.

Nonlinear dielectric and medium-amplitude oscillatory shear experiments resolve nearby relaxations that linear spectroscopies could not separate unambiguously.