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Flow-induced crystallization from solution: The relative effects of extension and shearing flow fields

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Abstract

Calculations have been performed to evaluate the relative effects of extensional and shearing flow fields on both the chain elongation and crystal nucleation rate enhancement for polyethylene crystallizing from xylene solutions. Rheological behavior was evaluated by means of the elastic dumbbell model modified for nonlinear effects at high elongations, and nucleation rate effects were considered from an essentially phenomenological view point. Molecular weight effects were also incorporated explicitly in the computations. Results show that chain elongation and nucleation rate enhancement is far greater for extensional than for shearing flows. Semiquantitative comparisons with experimental results reported in the literature for various aspects of the flow induced process, including the important fractionation effects, are discussed. Modification of the dumbbell model to account for shear rate effects on the intrinsic viscosity is also discussed.

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