A constitutive equation for Rouse model modified for variations of spring stiffness, bead friction, and Brownian force intensity under flow

Abstract

We derived a constitutive equation for the Rouse model (the most frequently utilized bead-spring model) with its spring constant κ, bead friction coefficient ζ, and the (squared) Brownian force intensity B being allowed to change under flow. Specifically, we modified the Langevin equation of the original Rouse model by introducing time (t)-dependent κ, ζ, and B (of arbitrary t dependence), which corresponded to the decoupling and preaveraging approximations often made in bead-spring models. From this modified Langevin equation, we calculated time evolution of second-moment averages of the Rouse eigenmode amplitudes and further converted this evolution into a constitutive equation. It turned out that the equation has a functional form, σ (t) = ∫ - ∞ t d t ′ { κ (t) / κ (t ′) } M (t, t ′) C - 1 (t, t ′), where σ (t) and C - 1 (t, t ′) are the stress and Finger strain tensors, and M (t, t ′) is the memory function depending on κ (t ′), ζ (t ′), and B (t ′) defined under flow. This equation, serving as a basis for analysis of nonlinear rheological behavior of unentangled melts, reproduces previous theoretical results under specific conditions, the Lodge-Wu constitutive equation for the case of t-independent κ, ζ, and B [A. S. Lodge and Y. Wu, "Constitutive equations for polymer solutions derived from the bead/spring model of Rouse and Zimm,"Rheol. Acta 10, 539 (1971)], the finite extensible nonlinear elastic (FENE)-Peterlin mean-Rouse formulation for the case of t-dependent changes of the only κ reported by Wedgewood and co-workers [L. E. Wedgewood et al., "A finitely extensible bead-spring chain model for dilute polymer solutions,"J. Non-Newtonian Fluid Mech. 40, 119 (1991)], and analytical expression of steady state properties for arbitrary κ (t), ζ (t), and B(t) reported by ourselves [H. Watanabe et al., "Revisiting nonlinear flow behavior of Rouse chain: Roles of FENE, friction reduction, and Brownian force intensity variation,"Macromolecules 54, 3700 (2021)]. It is to be added that a constitutive equation reported by Narimissa and Wagner [E. Narimissa and M. H. Wagner, "Modeling nonlinear rheology of unentangled polymer melts based on a single integral constitutive equation,"J. Rheol. 64, 129 (2020)] has a significantly different functional form and cannot be derived from the Rouse model with any simple modification of the Rouse-Langevin equation.