Rheology of a Supercooled Polymer Melt

Molecular dynamics simulations are performed for a polymer melt composed of short chains in quiescent and sheared conditions. The stress relaxation function $G(t)$ exhibits a stretched exponential form in a relatively early stage and ultimately follows the Rouse function in quiescent supercooled state. Transient stress evolution after application of shear obeys the linear growth $\int_0^t dt'G(t')$ for strain less than 0.1 and then saturates into a non-Newtonian viscosity. In steady states, strong shear-thinning and elongation of chains into ellipsoidal shapes are found at extremely small shear. A glassy component of the stress is much enhanced in these examples.Comment: 4 pages, 5 figure

Velocity relaxation of a particle in a confined compressible fluid

The velocity relaxation of an impulsively forced spherical particle in a fluid confined by two parallel plane walls is studied using a direct numerical simulation approach. During the relaxation process, the momentum of the particle is transmitted in the ambient fluid by viscous diffusion and sound wave propagation, and the fluid flow accompanied by each mechanism has a different character and affects the particle motion differently. Because of the bounding walls, viscous diffusion is hampered, and the accompanying shear flow is gradually diminished. However, the sound wave is repeatedly reflected and spreads diffusely. As a result, the particle motion is governed by the sound wave and backtracks differently in a bulk fluid. The time when the backtracking of the particle occurs changes non-monotonically with respect to the compressibility factor and is minimized at the characteristic compressibility factor. This factor depends on the wall spacing, and the dependence is different at small and large wall spacing regions based on the different mechanisms causing the backtracking.Comment: 8 pages, 9 figure

Synchronized molecular-dynamics simulation for the thermal lubrication of a polymeric liquid between parallel plates

The Synchronized Molecular-Dynamics simulation which was recently proposed by authors [Phys. Rev. X {\bf 4}, 041011 (2014)] is applied to the analysis of polymer lubrication between parallel plates. The rheological properties, conformational change of polymer chains, and temperature rise due to the viscous heating are investigated with changing the values of thermal conductivity of the polymeric liquid. It is found that at a small applied shear stress on the plate, the temperature of polymeric liquid only slightly increases in inverse proportion to the thermal conductivity and the apparent viscosity of polymeric liquid is not much affected by changing the thermal conductivity. However, at a large shear stress, the transitional behaviors of the polymeric liquid occur due to the interplay of the shear deformation and viscous heating by changing the thermal conductivity. This transition is characterized by the Nahme-Griffith number $Na$ which is defined as the ratio of the viscous heating to the thermal conduction at a characteristic temperature. When the Nahme-Griffith number exceeds the unity, the temperature of polymeric liquid increases rapidly and the apparent viscosity also exponentially decreases as the thermal conductivity decreases. The conformation of polymer chains is stretched and aligned by the shear flow for $Na<1$, but the coherent structure becomes disturbed by the thermal motion of molecules for $Na>1$.Comment: 19 pages, 3 figures. arXiv admin note: substantial text overlap with arXiv:1401.124

Replica-exchange molecular dynamics simulation for supercooled liquids

We investigate to what extend the replica-exchange Monte Carlo method is able to equilibrate a simple liquid in its supercooled state. We find that this method does indeed allow to generate accurately the canonical distribution function even at low temperatures and that its efficiency is about 10-100 times higher than the usual canonical molecular dynamics simulation.Comment: 6 pages, 5 figure

Lifetime of dynamical heterogeneity in a highly supercooled liquid

We numerically examine dynamical heterogeneity in a highly supercooled three-dimensional liquid via molecular-dynamics simulations. To define the local dynamics, we consider two time intervals, $\tau_\alpha$ and $\tau_{\text{ngp}}$. $\tau_\alpha$ is the $\alpha$ relaxation time, and $\tau_{\text{ngp}}$ is the time at which non-Gaussian parameter of the van Hove self-correlation function is maximized. We determine the lifetimes of the heterogeneous dynamics in these two different time intervals, $\tau_{\text{hetero}}(\tau_\alpha)$ and $\tau_{\text{hetero}}(\tau_{\text{ngp}})$, by calculating the time correlation function of the particle dynamics, i.e., the four-point correlation function. We find that the difference between $\tau_{\text{hetero}}(\tau_\alpha)$ and $\tau_{\text{hetero}}(\tau_{\text{ngp}})$ increases with decreasing temperature. At low temperatures, $\tau_{\text{hetero}}(\tau_\alpha)$ is considerably larger than $\tau_{\alpha}$, while $\tau_{\text{hetero}}(\tau_{\text{ngp}})$ remains comparable to $\tau_{\alpha}$. Thus, the lifetime of the heterogeneous dynamics depends strongly on the time interval.Comment: 4pages, 6figure

Tumbling motion of a single chain in shear flow: a crossover from Brownian to non-Brownian behavior

We present numerical results for the dynamics of a single chain in steady shear flow. The chain is represented by a bead-spring model, and the smoothed profile method is used to accurately account for the effects of thermal fluctuations and hydrodynamic interactions acting on beads due to host fluids. It is observed that the chain undergoes tumbling motions and that its dimensionless frequency F depends only on the Peclet number Pe with a power law. The exponent of Pe clearly changes from 2/3 to 1 around the critical Peclet number, indicating that the crossover reflects the competition of thermal fluctuation and shear flow. The presented numerical results agree well with our theoretical analysis based on Jeffery's work