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Universality of steady shear flow of Rouse melts

Poh, Leslie; Narimissa, Esmaeil; Wagner, Manfred H.

The data set of steady and transient shear data reported by Santangelo and Roland Journal of Rheology 45: 583–594, (2001) in the nonlinear range of shear rates of an unentangled polystyrene melt PS13K with a molar mass of 13.7 kDa is analysed by using the single integral constitutive equation approach developed by Narimissa and Wagner Journal of Rheology 64:129–140, (2020) for elongational and shear flow of Rouse melts. We compare model predictions with the steady-state, stress growth, and stress relaxation data after start-up shear flows. In characterising the linear-viscoelastic relaxation behaviour, we consider that in the vicinity of the glass transition temperature, Rouse modes and glassy modes are inseparable, and we model the terminal regime of PS13K by effective Rouse modes. Excellent agreement is achieved between model predictions and shear viscosity data, and good agreement with first normal stress coefficient data. In particular, the shear viscosity data of PS13K as well as of two polystyrene melts with M = 10.5 kDa and M = 9.8 kDa investigated by Stratton Macromolecules 5 (3): 304–310, (1972) agree quantitatively with the universal mastercurve predicted by Narimissa and Wagner for unentangled melts, and approach a scaling of Wi−1/2at sufficiently high Weissenberg numbers Wi. Some deviations between model predictions and data are seen for stress growth and stress relaxation of shear stress and first normal stress difference, which may be attributed to limitations of the experimental data, and may also indicate limitations of the model due to the complex interactions of Rouse modes and glassy modes in the vicinity of the glass transition temperature.
Published in: Rheologica Acta, 10.1007/s00397-020-01236-2, SpringerNature