The crossover between linear and non-linear mechanical behaviour in polymer solutions as detected by Fourier-transform rheology

The application of oscillatory shear strain leads, in the nonlinear regime, to the appearance of higher harmonic contributions in the shear stress response. These contributions can be analyzed as spectra in Fourier space, with respect to different frequencies, amplitudes and phase angles. In this article, we present an application of this new characterization method to a solution of the linear homopolymer polyisobutylene. The degree of nonlinear response during oscillatory shear is quantified using the normalized intensity of the third harmonic contribution. We were able to show experimentally on polyisobutylene that there is an immediate onset of the non-linear response even for very small shear strain amplitudes.