Interchain Pressure Effect in Extensional Flows of Entangled Polymer Melts

Abstract

Recent data by Hassager and co-workers [Bach et al. Macromolecules 2003, 36, 5174] of elongational viscosity of nearly monodisperse polystyrene melts are interpreted by including in the classical tube theories for entangled polymer dynamics an interchain repulsive contribution. The proposed theory predicts the observed power law of ηel vs ˘in a straightforward way and qualitatively explains the observed scaling with the polymer molecular mass. Possible generalizations are discussed.

Monte Carlo simulations of densely-packed athermal polymers in the bulk and under confinement

“…The latter is frequently used to link the theory with experimentally observed rheological properties of polymeric melts through its connection to the plateau modulus (Everaers et al, 2004;Fetters et al, 1999;Foteinopoulou et al, 2009;Theodorou and Tzoumanekas, 2006;Tzoumanekas et al, 2009). Additionally, the derived entanglement statistics can be mapped (Anogiannakis et al, 2012;Foteinopoulou et al, 2008;Steenbakkers et al, 2014) into novel slip-link theories that describe the rheological behaviour of polymeric liquids (Khaliullin and Schieber, 2009;Likhtman, 2005;Marrucci and Ianniruberto, 2004;Masubuchi et al, 2003;Ramirez et al, 2007;Stephanou et al, 2011;Wang et al, 2012).…”

“…This unique behaviour is intimately related to the uncrossability of chains which effectively leads to topological constraints between chains in the form of entanglements (deGennes, 1980;Doi and Edwards, 1988). The original reptation theory, based on the tube model, and more recent theoretical concepts have captured qualitatively and quantitatively the effect of entanglements on polymer dynamics and rheology (deGennes, 1980;Doi and Edwards, 1988;Kroger, 2004;Likhtman, 2005;Likhtman and McLeish, 2002;Marrucci, 1996;Marrucci and Ianniruberto, 2004;McLeish and Larson, 1998;Ramirez et al, 2007;Stephanou et al, 2011;Wang et al, 2012). Additionally, density is one of the key factors which affect profoundly the static, dynamic and rheological properties of entangled polymers (Daoud et al, 1975;Doi and Edwards, 1988;Edwards, 1966;Fleer et al, 1993).…”

Mechanism of spontaneous hole formation in thin polymeric films

“…12 While the original Doi and Edwards model 11 has many limitations, Wagner et al 13 added a stretch equation based on the "interchain pressure" concept. 14 This approach is currently the most accurate model to predict the flow behavior of monodisperse polymer melts. 13,15,16 The analytical model is…”

Experimental validation of a tube based constitutive equation for linear polymer melts with inter-chain tube pressure effect

“…Such behaviour was only predicted by previous models using unrealistically low values of the chain finite extensibility parameter [1,15]. A further model of interchain tube pressure effect was then proposed by Marrucci and Ianniruberto [17] to explain Bach et al [16] results, followed by macroscopic constitutive equations from Wagner et al [18] and Dhole et al [1] that were able to quantitatively predict them. The present study aimed at checking the validity of the model of Dhole et al in both rheometrical and complex flows, for a polydisperse polystyrene melt.…”

“…where θ is the reptation time (known to vary like Z 3 , Z being the number of entangled segments), θ R is the Rouse time (which varies like Z 2 ), θ p is the inter-chain pressure relaxation time (proportional to θ R , according to Marrucci and Ianniruberto [17]) and β is the convective constraint release parameter. The parameter β controls the rate of chains disentanglement in strong flows (i.e.…”