The Gordon–Schowalter/Johnson–Segalman model in parallel and orthogonal superposition rheometry and its application in the study of worm-like micellular systems

Parallel and Orthogonal Superposition experiments may be employed to probe a material's non-linear rheological properties through the rate-dependent parallel and orthogonal superposition moduli, G∥∗(ω,γ̇) and G⊥∗(ω,γ̇), respectively. In a recent series of publications, we have considered the problem of interconversion between parallel and orthogonal superposition moduli as a means of probing flow induced anisotropy. However, as noted by Yamomoto (1971) superposition flows may be used to assess the ability of a particular constitutive model to describe the flow of complex fluids. Herein, we derive expressions for the superposition moduli of the Gordon-Schowalter (or Johnson-Segalman) fluid. This model contains, as special cases, the corotational Maxwell model, the upper (and lower) convected Maxwell models, the corotational Jeffreys model, and the Oldroyd-B model. We also consider the conditions under which the superposition moduli may take negative values before studying a specific, non shear banding, worm like micellular system of cetylpyridinium chloride and sodium salicylate. We find that, using a weakly non-linear analysis (in which the model parameters are rate independent) the Gordon-Schowalter/Johnson-Segalman (GS/JS) model is unable to describe the superposition moduli. However, by permitting strong non-linearity (allowing the GS/JS parameters to become shear rate dependent), the superposition moduli, at all rates studied, are described well by the model. Based on this strongly non-linear anlaysis, the shear rate dependency of the GS/JS 'slip parameter', a, suggests that the onset of shear thinning in the specific worm-like micellular system studied herein is driven by a combination of microstructural modification and a transition from rotation dominated (as in the corotational Jeffreys model) to shear dominated (as in the Oldroyd-B model) deformation of the microstructural elements.