No Arabic abstract
We present a tube model for the Brownian dynamics of associating polymers in extensional flow. In linear response, the model confirms the analytical predictions for the sticky diffusivity by Leibler- Rubinstein-Colby theory. Although a single-mode DEMG approximation accurately describes the transient stretching of the polymers above a sticky Weissenberg number (product of the strain rate with the sticky-Rouse time), the pre-averaged model fails to capture a remarkable development of a power-law distribution of stretch in steady-state extensional flow: while the mean stretch is finite, the fluctuations in stretch may diverge. We present an analytical model that shows how strong stochastic forcing drive the long tail of the distribution, gives rise to rare events of reaching a threshold stretch and constitutes a framework within which nucleation rates of flow-induced crystallization may understood in systems of associating polymers under flow. The model also exemplifies a wide class of driven systems possessing strong, and scaling, fluctuations.
The sliding of non-Newtonian drops down planar surfaces results in a complex, entangled balance between interfacial forces and non linear viscous dissipation, which has been scarcely inspected. In particular, a detailed understanding of the role played by the polymer flexibility and the resulting elasticity of the polymer solution is still lacking. To this aim, we have considered polyacrylamide (PAA) solutions of different molecular weights, suspended either in water or glycerol/water mixtures. In contrast to drops with stiff polymers, drops with flexible polymers exhibit a remarkable elongation in steady sliding. This difference is most likely attributed to different viscous bending as a consequence of different shear thinning. Moreover, an optimal elasticity of the polymer seems to be required for this drop elongation to be visible. We have complemented experimental results with numerical simulations of a viscoelastic FENE-P drop. This has been a decisive step to unravel how a change of the elastic parameters (e.g. polymer relaxation time, maximum extensibility) affects the dimensionless sliding velocity.
Molecular dynamics simulations confirm recent extensional flow experiments showing ring polymer melts exhibit strong extension-rate thickening of the viscosity at Weissenberg numbers $Wi<<1$. Thickening coincides with the extreme elongation of a minority population of rings that grows with $Wi$. The large susceptibility of some rings to extend is due to a flow-driven formation of topological links that connect multiple rings into supramolecular chains. Links form spontaneously with a longer delay at lower $Wi$ and are pulled tight and stabilized by the flow. Once linked, these composite objects experience larger drag forces than individual rings, driving their strong elongation. The fraction of linked rings generated by flow depends non-monotonically on $Wi$, increasing to a maximum when $Wisim1$ before rapidly decreasing when the strain rate approaches the relaxation rate of the smallest ring loops $sim 1/tau_e$.
Based on discrete element method simulations, we propose a new form of the constitution equation for granular flows independent of packing fraction. Rescaling the stress ratio $mu$ by a power of dimensionless temperature $Theta$ makes the data from a wide set of flow geometries collapse to a master curve depending only on the inertial number $I$. The basic power-law structure appears robust to varying particle properties (e.g. surface friction) in both 2D and 3D systems. We show how this rheology fits and extends frameworks such as kinetic theory and the Nonlocal Granular Fluidity model.
Although the behavior of fluid-filled vesicles in steady flows has been extensively studied, far less is understood regarding the shape dynamics of vesicles in time-dependent oscillatory flows. Here, we investigate the nonlinear dynamics of vesicles in large amplitude oscillatory extensional (LAOE) flows using both experiments and boundary integral (BI) simulations. Our results characterize the transient membrane deformations, dynamical regimes, and stress response of vesicles in LAOE in terms of reduced volume (vesicle asphericity), capillary number ($Ca$, dimensionless flow strength), and Deborah number ($De$, dimensionless flow frequency). Results from single vesicle experiments are found to be in good agreement with BI simulations across a wide range of parameters. Our results reveal three distinct dynamical regimes based on vesicle deformation: pulsating, reorienting, and symmetrical regimes. We construct phase diagrams characterizing the transition of vesicle shapes between pulsating, reorienting, and symmetrical regimes within the two-dimensional Pipkin space defined by $De$ and $Ca$. Contrary to observations on clean Newtonian droplets, vesicles do not reach a maximum length twice per strain rate cycle in the reorienting and pulsating regimes. The distinct dynamics observed in each regime result from a competition between the flow frequency, flow time scale, and membrane deformation timescale. By calculating the particle stresslet, we quantify the nonlinear relationship between average vesicle stress and strain rate. Additionally, we present results on tubular vesicles that undergo shape transformation over several strain cycles. Broadly, our work provides new information regarding the transient dynamics of vesicles in time-dependent flows that directly informs bulk suspension rheology.
The tumbling dynamics of individual polymers in semidilute solution is studied by large-scale non-equilibrium mesoscale hydrodynamic simulations. We find that the tumbling time is equal to the non-equilibrium relaxation time of the polymer end-to-end distance along the flow direction and strongly depends on concentration. In addition, the normalized tumbling frequency as well as the widths of the alignment distribution functions for a given concentration-dependent Weissenberg number exhibit a weak concentration dependence in the cross-over regime from a dilute to a semidilute solution. For semidilute solutions a universal behavior is obtained. This is a consequence of screening of hydrodynamic interactions at polymer concentrations exceeding the overlap concentration.