Gaussian approximation for finitely extensible bead-spring chains with hydrodynamic interaction

The Gaussian Approximation, proposed originally by Ottinger [J. Chem. Phys., 90 (1) : 463-473, 1989] to account for the influence of fluctuations in hydrodynamic interactions in Rouse chains, is adapted here to derive a new mean-field approximation for the FENE spring force. This "FENE-PG" force law approximately accounts for spring-force fluctuations, which are neglected in the widely used FENE-P approximation. The Gaussian Approximation for hydrodynamic interactions is combined with the FENE-P and FENE-PG spring force approximations to obtain approximate models for finitely-extensible bead-spring chains with hydrodynamic interactions. The closed set of ODE's governing the evolution of the second-moments of the configurational probability distribution in the approximate models are used to generate predictions of rheological properties in steady and unsteady shear and uniaxial extensional flows, which are found to be in good agreement with the exact results obtained with Brownian dynamics simulations. In particular, predictions of coil-stretch hysteresis are in quantitative agreement with simulations' results. Additional simplifying diagonalization-of-normal-modes assumptions are found to lead to considerable savings in computation time, without significant loss in accuracy.Comment: 26 pages, 17 figures, 2 tables, 75 numbered equations, 1 appendix with 10 numbered equations Submitted to J. Chem. Phys. on 6 February 200

The relationship between induced fluid structure and boundary slip in nanoscale polymer films

The molecular mechanism of slip at the interface between polymer melts and weakly attractive smooth surfaces is investigated using molecular dynamics simulations. In agreement with our previous studies on slip flow of shear-thinning fluids, it is shown that the slip length passes through a local minimum at low shear rates and then increases rapidly at higher shear rates. We found that at sufficiently high shear rates, the slip flow over atomically flat crystalline surfaces is anisotropic. It is demonstrated numerically that the friction coefficient at the liquid-solid interface (the ratio of viscosity and slip length) undergoes a transition from a constant value to the power-law decay as a function of the slip velocity. The characteristic velocity of the transition correlates well with the diffusion velocity of fluid monomers in the first fluid layer near the solid wall at equilibrium. We also show that in the linear regime, the friction coefficient is well described by a function of a single variable, which is a product of the magnitude of surface-induced peak in the structure factor and the contact density of the adjacent fluid layer. The universal relationship between the friction coefficient and induced fluid structure holds for a number of material parameters of the interface: fluid density, chain length, wall-fluid interaction energy, wall density, lattice type and orientation, thermal or solid walls.Comment: 33 pages, 14 figure

Semiflexible polymers under external fields confined to two dimensions

The non-equilibrium structural and dynamical properties of semiflexible polymers confined to two dimensions are investigated by molecular dynamics simulations. Three different scenarios are considered: The force-extension relation of tethered polymers, the relaxation of an initially stretched semiflexible polymer, and semiflexible polymers under shear flow. We find quantitative agreement with theoretical predictions for the force-extension relation and the time dependence of the entropically contracting polymer. The semiflexible polymers under shear flow exhibit significant conformational changes at large shear rates, where less stiff polymers are extended by the flow, whereas rather stiff polymers are contracted. In addition, the polymers are aligned by the flow, thereby the two-dimensional semiflexible polymers behave similarly to flexible polymers in three dimensions. The tumbling times display a power-law dependence at high shear rate rates with an exponent comparable to the one of flexible polymers in three-dimensional systems.Comment: Accepted for publication in J. Chem. Phy

Polymeric filament thinning and breakup in microchannels

The effects of elasticity on filament thinning and breakup are investigated in microchannel cross flow. When a viscous solution is stretched by an external immiscible fluid, a low 100 ppm polymer concentration strongly affects the breakup process, compared to the Newtonian case. Qualitatively, polymeric filaments show much slower evolution, and their morphology features multiple connected drops. Measurements of filament thickness show two main temporal regimes: flow- and capillary-driven. At early times both polymeric and Newtonian fluids are flow-driven, and filament thinning is exponential. At later times, Newtonian filament thinning crosses over to a capillary-driven regime, in which the decay is algebraic. By contrast, the polymeric fluid first crosses over to a second type of flow-driven behavior, in which viscoelastic stresses inside the filament become important and the decay is again exponential. Finally, the polymeric filament becomes capillary-driven at late times with algebraic decay. We show that the exponential flow thinning behavior allows a novel measurement of the extensional viscosities of both Newtonian and polymeric fluids.Comment: 7 pages, 7 figure

Thermodiffusion in model nanofluids by molecular dynamics simulations

In this work, a new algorithm is proposed to compute single particle (infinite dilution) thermodiffusion using Non-Equilibrium Molecular Dynamics simulations through the estimation of the thermophoretic force that applies on a solute particle. This scheme is shown to provide consistent results for simple Lennard-Jones fluids and for model nanofluids (spherical non-metallic nanoparticles + Lennard-Jones fluid) where it appears that thermodiffusion amplitude, as well as thermal conductivity, decrease with nanoparticles concentration. Then, in nanofluids in the liquid state, by changing the nature of the nanoparticle (size, mass and internal stiffness) and of the solvent (quality and viscosity) various trends are exhibited. In all cases the single particle thermodiffusion is positive, i.e. the nanoparticle tends to migrate toward the cold area. The single particle thermal diffusion 2 coefficient is shown to be independent of the size of the nanoparticle (diameter of 0.8 to 4 nm), whereas it increases with the quality of the solvent and is inversely proportional to the viscosity of the fluid. In addition, this coefficient is shown to be independent of the mass of the nanoparticle and to increase with the stiffness of the nanoparticle internal bonds. Besides, for these configurations, the mass diffusion coefficient behavior appears to be consistent with a Stokes-Einstein like law

Supersymmetry solution for finitely extensible dumbbell model

Exact relaxation times and eigenfunctions for a simple mechanical model of polymer dynamics are obtained using supersymmetry methods of quantum mechanics. The model includes the finite extensibility of the molecule and does not make use of the self-consistently averaging approximation. The finite extensibility reduces the relaxation times when compared to a linear force. The linear viscoelastic behaviour is obtained in the form of the ``generalized Maxwell model''. Using these results, a numerical integration scheme is proposed in the presence of a given flow kinematics.Comment: 5 pages, 2 figure

Interfacial friction between semiflexible polymers and crystalline surfaces

The results obtained from molecular dynamics simulations of the friction at an interface between polymer melts and weakly attractive crystalline surfaces are reported. We consider a coarse-grained bead-spring model of linear chains with adjustable intrinsic stiffness. The structure and relaxation dynamics of polymer chains near interfaces are quantified by the radius of gyration and decay of the time autocorrelation function of the first normal mode. We found that the friction coefficient at small slip velocities exhibits a distinct maximum which appears due to shear-induced alignment of semiflexible chain segments in contact with solid walls. At large slip velocities the decay of the friction coefficient is independent of the chain stiffness. The data for the friction coefficient and shear viscosity are used to elucidate main trends in the nonlinear shear rate dependence of the slip length. The influence of chain stiffness on the relationship between the friction coefficient and the structure factor in the first fluid layer is discussed.Comment: 31 pages, 12 figure

The effects of organic farming on the soil physical environment

The aim of this research was to investigate the effects of organic farming practices on the development of soil physical properties, and in particular, soil structure in comparison with conventional agricultural management. The soil structure of organically and conventionally managed soils at one site was compared in a quantitative manner at different scales of observations using image analysis. Key soil physical and chemical properties were measured as well as the pore fractal geometry to characterise pore roughness. Organically managed soils had higher organic matter content and provided a more stable soil structure than conventionally managed soils. The higher porosity (%) at the macroscale in soil under conventional management was due to fewer larger pores while mesoand microscale porosity was found to be greater under organic management. Organically managed soils typically provided spatially well distributed pores of all sizes and of greater roughness compared to those under conventional management. These variations in the soil physical environment are likely to impact significantly on the performance of these soils for a number of key processes such as crop establishment and water availabilit

Dewetting dynamics of stressed viscoelastic thin polymer films

Ultrathin polymer films that are produced e.g. by spin-coating are believed to be stressed since polymers are 'frozen in' into out-of-equilibrium configurations during this process. In the framework of a viscoelastic thin film model, we study the effects of lateral residual stresses on the dewetting dynamics of the film. The temporal evolution of the height profiles and the velocity profiles inside the film as well as the dissipation mechanisms are investigated in detail. Both the shape of the profiles and the importance of frictional dissipation vs. viscous dissipation inside the film are found to change in the course of dewetting. The interplay of the non-stationary profiles, the relaxing initial stress and changes in the dominance of the two dissipation mechanisms caused by nonlinear friction with the substrate is responsible for the rich behavior of the system. In particular, our analysis sheds new light on the occurrence of the unexpected maximum in the rim width obtained recently in experiments on PS-PDMS systems.Comment: 11 pages, 10 figure

Flow pattern transition accompanied with sudden growth of flow resistance in two-dimensional curvilinear viscoelastic flows

We find three types of steady solutions and remarkable flow pattern transitions between them in a two-dimensional wavy-walled channel for low to moderate Reynolds (Re) and Weissenberg (Wi) numbers using direct numerical simulations with spectral element method. The solutions are called "convective", "transition", and "elastic" in ascending order of Wi. In the convective region in the Re-Wi parameter space, the convective effect and the pressure gradient balance on average. As Wi increases, the elastic effect becomes suddenly comparable and the first transition sets in. Through the transition, a separation vortex disappears and a jet flow induced close to the wall by the viscoelasticity moves into the bulk; The viscous drag significantly drops and the elastic wall friction rises sharply. This transition is caused by an elastic force in the streamwise direction due to the competition of the convective and elastic effects. In the transition region, the convective and elastic effects balance. When the elastic effect dominates the convective effect, the second transition occurs but it is relatively moderate. The second one seems to be governed by so-called Weissenberg effect. These transitions are not sensitive to driving forces. By the scaling analysis, it is shown that the stress component is proportional to the Reynolds number on the boundary of the first transition in the Re-Wi space. This scaling coincides well with the numerical result.Comment: 33pages, 23figures, submitted to Physical Review