• Korea-Australia Rheology Journal
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• v.21 no.4
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• pp.203-211
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• 2009

In flows with deformation rates larger than the inverse Rouse time of the polymer chain, chains are stretched and their confining tubes become increasingly anisotropic. The pressures exerted by a polymer chain on the walls of an anisotropic confinement are anisotropic and limit chain stretch. In the Molecular Stress Function (MSF) model, chain stretch is balanced by an interchain pressure term, which is inverse proportional to the $3^{rd}$ power of the tube diameter and is characterized by a tube diameter relaxation time. We show that the tube diameter relaxation time is equal to 3 times the Rouse time in the limit of small chain stretch. At larger deformations, we argue that chain stretch is balanced by two restoring tensions with weights of 1/3 in the longitudinal direction of the tube (due to a linear spring force) and 2/3 in the lateral direction (due to the nonlinear interchain pressure), both of which are characterized by the Rouse time. This approach is shown to be in quantitative agreement with transient and steady-state elongational viscosity data of two monodisperse polystyrene melts without using any nonlinear parameter, i.e. solely based on the linear-viscoelastic characterization of the melts. The same approach is extended to model experimental data of four styrene-butadiene random copolymer melts in shear flow. Thus for monodisperse linear polymer melts, for the first time a constitutive equation is presented which allows quantitative modeling of nonlinear extension and shear rheology on the basis of linear-viscoelastic data alone.

• Korea-Australia Rheology Journal
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• v.14 no.1
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• pp.33-45
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• 2002

Recent results obtained for the port-pom model and the constitutive equations with time-strain separability are examined. The time-strain separability in viscoelastic systems Is not a rule derived from fundamental principles but merely a hypothesis based on experimental phenomena, stress relaxation at long times. The violation of separability in the short-time response just after a step strain is also well understood (Archer, 1999). In constitutive modeling, time-strain separability has been extensively employed because of its theoretical simplicity and practical convenience. Here we present a simple analysis that verifies this hypothesis inevitably incurs mathematical inconsistency in the viewpoint of stability. Employing an asymptotic analysis, we show that both differential and integral constitutive equations based on time-strain separability are either Hadamard-type unstable or dissipative unstable. The conclusion drawn in this study is shown to be applicable to the Doi-Edwards model (with independent alignment approximation). Hence, the Hadamardtype instability of the Doi-Edwards model results from the time-strain separability in its formulation, and its remedy may lie in the transition mechanism from Rouse to reptational relaxation supposed by Doi and Edwards. Recently in order to describe the complex rheological behavior of polymer melts with long side branches like low density polyethylene, new constitutive equations called the port-pom equations have been derived in the integral/differential form and also in the simplifled differential type by McLeish and carson on the basis of the reptation dynamics with simplifled branch structure taken into account. In this study mathematical stability analysis under short and high frequency wave disturbances has been performed for these constitutive equations. It is proved that the differential model is globally Hadamard stable, and the integral model seems stable, as long as the orientation tensor remains positive definite or the smooth strain history in the flow is previously given. However cautious attention has to be paid when one employs the simplified version of the constitutive equations without arm withdrawal, since neglecting the arm withdrawal immediately yields Hadamard instability. In the flow regime of creep shear flow where the applied constant shear stress exceeds the maximum achievable value in the steady flow curves, the constitutive equations exhibit severe instability that the solution possesses strong discontinuity at the moment of change of chain dynamics mechanisms.

• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1595-1603
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• 2002

In this paper we have presented the results of diffusion behavior of model systems for eight liquid n-alkanes ($C_{12}$-$C_{44}$) in a canonical (NVT) ensemble at several temperatures using molecular dynamics simulations. For these n-alkanes of small chain length n, the chains are clearly <$R_{ee}^2$>/6<$R_g^2$>>1 and non-Gaussian. This result implies that the liquid n-alkanes over the whole temperatures considered are far away from the Rouse regime, though the ratio becomes close to the unity as n increases. Calculated self-diffusion constants $D_{self}$ are comparable with experimental results and the Arrhenius plot of self-diffusion constants versus inverse temperature shows a different temperature dependence of diffusion on the chain length. The global rotational motion of n-alkanes is examined by characterizing the orientation relaxation of the end-to-end vector and it is found that the ratio ${\tau}1/{\tau}2$ is less than 3, the value expected for a isotropically diffusive rotational process. The friction constants ${\xi}$of the whole molecules of n-alkanes are calculated directly from the force auto-correlation (FAC) functions and compared with the monomeric friction constants ${\xi}_D$ extracted from $D_{self}$. Both the friction constants give a correct qualitative trends: decrease with increasing temperature and increase with increasing chain length. The friction constant calculated from the FAC's decreases very slowly with increasing temperature, while the monomeric friction constant varies rapidly with temperature. By considering the orientation relaxation of local vectors and diffusion of each site, it is found that rotational and translational diffusions of the ends are faster than those of the center.