The rheological and optical properties of dilute polymer solutions during the startup and subsequent relaxation in exponential shear flow are studied using Brownian dynamics simulations of freely draining, flexible bead-rod chains. We find that exponential shear flow is capable of effecting large molecular deformation for finite shear rates and strains, and furthermore, the polymer undergoes an initial stress and index of refraction relaxation that is much faster than a single exponential decay upon cessation of flow. When we compare the first normal stress difference ( τ 11– τ 22) to the corresponding components of the index of refraction tensor, n 11– n 22, we find that there is hysteresis when plotted over the course of a full startup and relaxation experiment. This is very similar to the hysteresis originally discovered by Doyle et al. [J. Non-Newtonian Fluid Mech. 76 (1998) 79–110] for uniaxial extensional flow. Moreover, the shear components of the stress and index of refraction tensors ( τ 12 and n 12) also exhibit hysteretic behavior. However, whereas the hysteresis loop for the 11–22 component traverses up the left branch during startup and relaxes on the right branch, that for the 12 component is in the completely opposite direction, i.e. the right branch corresponds to startup and the left branch relaxation. The presence of stress-index of refraction hysteresis clearly has important implications for the stress-optic rule. We calculate the stress-optic coefficient for the startup process, and find that the normal and shear components give the same value, but that it is strongly dependent on Wi. This result is consistent with that found by Doyle et al. during the startup of steady shear flow [Doyle and Shaqfeh, Dynamic simulation of freely-draining, flexible bead-rod chains: startup of extensional and shear flow, J. Non-Newtonian Fluid Mech. 76 (1998) 43–78]. We also simulated shear flows with a linearly ramped shear rate to compare to our results for exponential shear. We find that for comparable final shear rate and time, both exponential and linear ramping shear produce very similar hysteresis effects in both the shear and normal components suggesting that there may be many unsteady shear flow capable of creating large polymer stretch and stress-birefringence hysteresis. Finally, we compare our bead-rod chain simulations to the FENE dumbbell model, and we find that while the latter can qualitatively capture the normal stress hysteresis, it predicts negligible shear stress hysteresis at equivalent shear rates and shear strains.
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