Abstract
Transient elongational flow was created by forcing dilute PS solutions across a narrow contraction. Rheo-optical measurements revealed a localized birefringence zone above a critical strain-rate in the immediate orifice entrance. Birefringence was studied with a polarization-modulation technique for dilute PS solutions (50–500 ppm) as a function of fluid flow rate (1000-38000 s-1), polymer molecular weight (M = 1.93–24 • 106) and solvent quality (decalin and 1-methyl-naphthalene). Transient elongational flow is complicated by the presence of local orientation distribution along the different streamlines. To account for this effect, a numerical technique has been devised to compute local birefringence (An) from experimental retardation (δ). Orientation correction turned out to be unimportant except at the dosest distances from orifice entrance. Results show a steep decrease in birefringence with axial distance. Birefringence profiles determined in a direction perpendicular to the flow show a maximum, not at the center, but in the vicinity of the orifice walls. This effect was explained by means of flow simulation which indicated the presence of extreme strain rates near re-entrant corners. Molecular extension ratio calculated with the Kuhn-Grün theory suggests that polymers may uncoil up to one third of the chain contour length at the approach of capillary entrance. Notable departure from the affine deformation model is, however, observed with multiple birefringence saturation levels changing with flow rate conditions.
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Nguyen, T.Q., Porouchani, R., Kausch, HH. (1999). Birefringence of Dilute PS Solutions in Abrupt Contraction Flow. In: Nguyen, T.Q., Kausch, HH. (eds) Flexible Polymer Chains in Elongational Flow. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-58252-3_8
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