A stretch-based model for flow-enhanced nucleation of polymer melts

R.J.A. Steenbakkers, G.W.M. Peters

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Abstract

A phenomenological model for flow-enhanced nucleation in crystallizing polymers is developed and validated by short-term shear experiments from Hristova, Peters et al. (2004) and Housmans, Steenbakkers et al. (2009). The model extends earlier work on flow-induced oriented crystallization [ Custodio, Steenbakkers et al. (2009); Peters (2003); Peters, Swartjes et al. (2002); Swartjes, Peters et al. (2003); Zuidema (2000); Zuidema, Peters et al. (2001)] to flow-enhanced pointlike nucleation, which can lead to number densities of spherulites multiplied by orders of magnitude. Excellent agreement between simulations and experimental data is obtained with only two free parameters: a prefactor to the creation rate of flow-induced nucleation precursors and a parameter that governs their influence on the relaxation dynamics of the high molecular weight (HMW) fraction of the melt. The two main conclusions of this paper are, first, that the creation of flow-induced precursors is driven by stretch, not by orientation, of the primitive path of chains in the HMW tail of the molecular weight distribution, and secondly, that nucleation of theseprecursors is impeded by flow.
Original languageEnglish
Pages (from-to)401-433
Number of pages33
JournalJournal of Rheology
Volume55
Issue number2
DOIs
Publication statusPublished - 2011

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