Kramers-Kronig Relations for Nonlinear Rheology: 2. Validation of Medium Amplitude Oscillatory Shear (MAOS) Measurements

Abstract

The frequency dependence of third-harmonic medium amplitude oscillatory shear (MAOS) modulus $G_{33}^{*}(\omega)$ provides insight into material behavior and microstructure in the asymptotically nonlinear regime. Motivated by the difficulty in the measurement of MAOS moduli, we propose a test for data validation based on nonlinear Kramers-Kronig relations. We extend the approach used to assess the consistency of linear viscoelastic data by expressing the real and imaginary parts of $G_{33}^{*}(\omega)$ as a linear combination of Maxwell elements: the functional form for the MAOS kernels is inspired by time-strain separability (TSS). We propose a statistical fitting technique called the SMEL test, which works well on a broad range of materials and models including those that do not obey TSS. It successfully copes with experimental data that are noisy, or confined to a limited frequency range. When Maxwell modes obtained from the SMEL test are used to predict the first-harmonic MAOS modulus $G_{31}^{*}$, it is possible to identify the range of timescales over which a material exhibits TSS.