New measures for characterizing nonlinear viscoelasticity in large amplitude oscillatory shear

Characterizing purely viscous or purely elastic rheological nonlinearities is straightforward using rheometric tests such as steady shear or step strains. However, a definitive framework does not exist to characterize materials which exhibit both viscous and elastic nonlinearities simultaneously. We define a robust and physically meaningful scheme to quantify such behavior, using an imposed large amplitude oscillatory shear (LAOS) strain. Our new framework includes new material measures and clearly defined terminology such as intra-/intercycle nonlinearities, strain-stiffening/softening, and shear-thinning/thickening. The method naturally lends a physical interpretation to the higher Fourier coefficients that are commonly reported to describe the nonlinear stress response. These nonlinear viscoelastic properties can be used to provide a "rheological fingerprint" in a Pipkin diagram that characterizes the material response as a function of both imposed frequency and strain amplitude. We illustrate our new framework by first examining prototypical nonlinear constitutive models (including purely elastic and purely viscous models, and the nonlinear viscoelastic constitutive equation proposed by Giesekus). In addition, we use this new framework to study experimentally two representative nonlinear soft materials, a biopolymer hydrogel and a wormlike micelle solution. These new material measures can be used to characterize the rheology of any complex fluid or soft solid and clearly reveal important nonlinear material properties which are typically obscured by conventional test protocols.