Constitutive model fingerprints in medium-amplitude oscillatory shear.

Rheologists have expectations for signatures of linear viscoelastic properties, such as shapes of G'(ω) and G?(ω). Medium amplitude (or asymptotically-nonlinear) oscillatory shear (MAOS) provides additional nonlinear rheological information with low dimensional, well-defined material functions [Ewoldt and Bharadwaj, Rheol. Acta 52, 201-209 (2013)]. Here, we develop expectations of signatures (or fingerprints) for the four asymptotically-nonlinear material functions associated with MAOS, [e1](ω), [e3](ω), [v1](ω), [v3](ω). Although the linear fingerprints may be identical for different models, the asymptotically-nonlinear fingerprints may be different in magnitude, frequency-scaling, curve shapes, and sign changes. To perform the analysis, we collect/translate a library of available analytical strain-controlled MAOS fingerprints for seven different constitutive models. Using this library, we identify general trends and highlight key differences of asymptotic-nonlinear viscoelasticity. Asymptotic nonlinearities for all models considered here obey the terminal regime inter-relations and frequency scaling predicted by Bharadwaj and Ewoldt [J. Rheol. 58, 891-910 (2014)]. Unlike the positive linear viscoelastic measures, at least one of the four asymptotic nonlinearities changes signs with Deborah number (De). Following sign interpretations of Ewoldt and Bharadwaj [Rheol. Acta 52, 201-209 (2013)], we show that nonlinearities tend to be driven by strain-rates at small De, and by strains at large De, a trend observed for nearly all the constitutive models studied here, the exception being the model for dilute rigid dumbbell suspensions of Bird et al. [J. Chem. Phys. 140, 074904 (2014)]. Some constitutive models exhibit multiple sign changes at intermediate De and there may be no universal behavior of asymptotically-nonlinear fingerprints in this regime. Therefore, frequency-dependent signatures can be material-specific. This will allow inverse problems to infer structure, select models, and fit model parameters using asymptotically-nonlinear signatures. To illustrate this aspect, we demonstrate a fingerprint matching exercise with experimental measurements on a transiently cross-linked hydrogel system. We find that currently available model fingerprints can match the qualitative magnitudes and frequency dependence, but not the signs of the experimental transient network response. [ABSTRACT FROM AUTHOR]