Concept of Stretch/Orientation-Induced Friction Reduction Tested with a Simple Molecular Constitutive Equation

抄録

Under elongational flow at strain rates higher than the Rouse relaxation frequency, entangled polymer melts exhibit thinning of their elongational viscosity whereas equally entangled solutions show thickening. Yaoita et al. [Yaoita et al., Macromolecules 2012, 45, 2773] related this difference between the melts and solutions to reduction of segmental friction on enhancement of the stretch/orientation averaged for the components therein (that includes the solvent for the case of solutions). They analyzed the stress relaxation data after cessation of elongational flow to propose an empirical equation describing this friction reduction as a function of the stretch/orientation factor. Multi-chain slip-link (PCN) simulations considering this friction reduction described the thinning of melts and the thickening of solutions consistently and semi-quantitatively. This study further tests the molecular concept of the stretch/orientation-induced friction reduction with the aid of a simple molecular constitutive equation, a toy version of the Mead-Larson-Doi model [Mead et al., Macromolecules 1998, 31, 7895] (MLD toy model) being modified to incorporate this empirical equation of the friction reduction. The modified toy model mimicked the behavior of melts and solutions consistently. This consistency vanished when the friction reduction in the model was artificially switched off, even though the finite extensible nonlinear elasticity was still taken into account. These results lend further support to the molecular concept of the stretch/orientation-induced friction reduction.