Despite decades of research, the question of whether solutions and melts of highly entangled polymers exhibit shear banding as their steady state response to a steadily imposed shear flow remains controversial. From a theoretical viewpoint, an important unanswered question is whether the underlying constitutive curve of shear stress $σ$ as a function of shear rate $\dotγ$ (for states of homogeneous shear) is monotonic, or has a region of negative slope, $dσ/d\dotγ<0$, which would trigger banding. Attempts to settle the question experimentally via velocimetry of the flow field inside the fluid are often confounded by an instability of the free surface where the sample meets the outside air, known as "edge fracture". Here we show by numerical simulation that in fact even only very modest edge disturbances - which are the precursor of full edge fracture but might well, in themselves, go unnoticed experimentally - can cause strong secondary flows in the form of shear bands that invade deep into the fluid bulk. Crucially, this is true even when the underlying constitutive curve is monotonically increasing, precluding true bulk shear banding in the absence of edge effects.
Based on numerical modeling with the diffusive Giesekus constitutive equation, a recent Letter [Phys. Rev. Lett. 120, 138002 (2018), arXiv:1801.08798] claimed that the experimental reports of shear banding in entangled polymeric fluids were due to the disturbances from the sample edge. The conclusion that true bulk shear banding is precluded in the presence of edge effects is at odds with many past experimental, theoretical, numerical, and computer simulation studies. We briefly discuss some problems of this work.
Edge instabilities are believed to be one of the possible causes of shear banding in entangled polymeric fluids. Here, we investigate the effect of edge disturbance on the shear-induced dynamics of well-entangled DNA solutions. Using a custom high-aspect-ratio planar-Couette cell, we systematically measure the velocity profiles of sheared DNA samples at different distances away from the edge of the shear cell. Under a weak oscillatory shear with the corresponding Weissenberg number (Wi) smaller than 1, where DNA solutions exhibit linear velocity profiles with strong wall slip, the penetration …
Even in simple geometries many complex fluids display non-trivial flow fields, with regions where shear is concentrated. The possibility for such shear banding has been known since several decades, but the recent years have seen an upsurge of studies offering an ever more precise understanding of the phenomenon. The development of new techniques to probe the flow on multiple scales and with increasing spatial and temporal resolution has opened the possibility for a synthesis of the many phenomena that could only have been thought of separately before. In this review, we bring together recent r…
Spatially inhomogeneous shear flow occurs in entangled polymer solutions, both as steady state shear banding and transiently after a large step strain or during start up to a steady uniform shear rate. Steady state shear banding is a hallmark of models with a non-monotonic constitutive relation between total shear stress and applied shear rate, but transient banding is sometimes seen in fluids that do not shear band at steady state. We model this behavior using the diffusive Rolie-Poly model in a Newtonian solvent, whose constitutive behavior can be monotonic or non-monotonic depending on the …
Using high-resolution confocal rheometry, we study the shear profiles of well-entangled DNA solutions under large amplitude oscillatory shear (LAOS) in a rectilinear planar shear cell. With increasing Weissenberg number (Wi), we observe successive transitions from normal Newtonian linear shear profiles to wall-slip dominant shear profiles and finally to shear-banding profiles at high Wi. To investigate the microscopic origin of the observed shear banding, we study the dynamics of micron-sized tracers embedded in DNA solutions. Surprisingly, tracer particles in the shear frame exhibit transient…
We study theoretically the formation of shear bands in time-dependent flows of polymeric and wormlike micellar surfactant fluids, focussing on the protocols of step shear stress, step shear strain (or in practice a rapid strain ramp), and shear startup, which are commonly studied experimentally. For each protocol we perform a linear stability analysis to provide a fluid-universal criterion for the onset of shear banding, following our recent Letter [Phys. Rev. Lett. 110 (2013) 086001]. In each case this criterion depends only on the shape of the experimentally measured rheological response fun…
Within a highly generalised theoretical framework for the flow properties of complex fluids, we study the onset of shear banding in the three most common time-dependent experimental protocols: step stress, step strain and shear startup. By means of a linear stability analysis we derive a fluid-universal criterion for the onset of banding, separately for each protocol, that depends only on the shape of the experimentally measured time-dependent rheological response function, independent of the constitutive law and internal state variables of the particular fluid in question. Our predictions thu…
Wang [Phys. Rev. Lett. 103, 219801 (2009)] makes the following points about our Letter [Phys. Rev. Lett. 102, 067801 (2009), arXiv:0805.0679]: (1) He infers that, "contrary to its title, shear banding emerged from monotonic curves only if there was a stress gradient", and he points out that nonquiescent relaxation was found (experimentally) after step strain in geometries without a stress gradient. (2) He disagrees with the values of the parameters we used. (3) In some recent experiments the flow was homogeneous after cessation of step strain, and only subsequently developed nonquiescent macro…
Recent step strain experiments in well-entangled polymeric liquids demonstrated a bulk fracture-like phenomenon. We have studied this instability using a modern version of the Doi-Edwards theory for entangled polymers, and we find close quantitative agreement with the experiments. The phenomenon occurs because the viscoelastic liquid is sheared into a rubbery state that possesses an elastic constitutive instability (Marrucci and Grizzuti, 1983). The fracture is a transient manifestation of this instability, which relies on the amplification of spatially inhomogeneous fluctuations. This mechani…
We investigate theoretically shear banding in large amplitude oscillatory shear (LAOS) of polymers and wormlike micelles. In LAOStrain we find banding at low frequencies and sufficiently high strain rate amplitudes in fluids for which the underlying constitutive curve of shear stress as a function of shear rate is non-monotonic. This is the direct analogue of quasi steady state banding seen in slow strain rate sweeps along the flow curve. At higher frequencies and sufficiently high strain amplitudes we report a different but related phenomenon, which we call `elastic' shear banding. This is as…
Edge fracture occurs frequently in non-Newtonian fluids. A similar instability has often been reported at the free surface of fluids undergoing shear banding, and leads to expulsion of the sample. In this paper the distortion of the free surface of such a shear banding fluid is calculated by balancing the surface tension against the second normal stresses induced in the two shear bands, and simultaneously requiring a continuous and smooth meniscus. We show that wormlike micelles typically retain meniscus integrity when shear banding, but in some cases can lose integrity for a range of average …
We report observations of a remarkable scaling behavior with respect to concentration in the passive microbead rheology of two highly entangled polymeric solutions, polyethylene oxide (PEO) and hyaluronic acid (HA). This behavior was reported previously [Hill et al., PLOS ONE (2014)] for human lung mucus, a complex biological hydrogel, motivating the current study for synthetic polymeric solutions PEO and HA. The strategy is to identify, and focus within, a wide range of lag times $τ$ for which passive micron diameter beads exhibit self-similar (fractional, power law) mean-squared-displacement…
This study focuses on comparing the individual polymer chain dynamics in an entangled polymeric liquid under different shear and extension rates. Polymer chains under various shear rates and extension rates were simulated using a stochastic-tube model [J. Rheol. 56: 1057 (2012)]. We developed a Matlab code to visualize and analyze the simulated configurations from the stochastic-tube model. We introduced new variables to determine how the extent of linearity changes with time for different shear rates, which is more useful than a typical end-to-end distance analysis. We identified whether the …
The interplay between shear band (SB) formation and boundary conditions (BC) is investigated in wormlike micellar systems (CPyCl--NaSal) using ultrasonic velocimetry coupled to standard rheology in Couette geometry. Time-resolved velocity profiles are recorded during transient strain-controlled experiments in smooth and sand-blasted geometries. For stick BC standard SB is observed, although depending on the degree of micellar entanglement temporal fluctuations are reported in the highly sheared band. For slip BC wall slip occurs only for shear rates larger than the start of the stress plateau.…
Understanding how entanglements affect the behaviour of polymeric complex fluids is an open challenge in many fields. To elucidate the nature and consequence of entanglements in dense polymer solutions, we propose a novel method: a "dynamical entanglement analysis" (DEA) to extract spatio-temporal entanglement structures from the pair-wise displacement correlation of entangled chains. By applying this method to large-scale Molecular Dynamics simulations of linear and unknotted, nonconcatenated ring polymers, we find a strong and unexpected cooperative dynamics: the footprint of mutual entrainm…
We use a hybrid method that combines the Multiparticle collision dynamics (MPCD) for solvent particles with the molecular dynamics for equilibrium polymers to simulate the shearing of the equilibrium polymers (or Wormlike micelles) at a mesoscopic length scale. The MPCD method incorporates the hydrodynamic interaction with the polymeric chains. We show successful implementation of the method on the model equilibrium polymers (or Wormlike micelles) and observe that the order of the Iso-Nem transition of the polymeric system is affected by the shear rate. Moreover, the chains of the equilibrium …
A mesoscopic, mixed particle- and field-based Brownian dynamics methodology for the simulation of entangled polymer melts has been developed. Polymeric beads consist of several Kuhn segments, and their motion is dictated by the Helmholtz energy of the sample, which is a sum of the entropic elasticity of chain strands between beads, slip springs, and nonbonded interactions. The entanglement effect is introduced by the slip springs, which are springs connecting either nonsuccessive beads on the same chain or beads on different polymer chains. The terminal positions of slip springs are altered du…
We briefly review the recent advances in the rheology of entangled polymers and identify emerging research trends and outstanding challenges, especially with respect to branched polymers. Emphasis is placed on the role of well-characterized model systems, as well as the synergy of synthesis-characterization, rheometry and modeling/simulations. The theoretical framework for understanding the observed linear and nonlinear rheological phenomena is the tube model which is critically assessed in view of its successes and shortcomings, whereas alternative approaches are briefly discussed. Finally, i…
Understanding and controlling the rheology of polymeric complex fluids that are pushed out-of-equilibrium is a fundamental problem in both industry and biology. For example, to package, repair, and replicate DNA, cells use enzymes to constantly manipulate DNA topology, length, and structure. Inspired by this, here we engineer and study DNA-based complex fluids that undergo enzymatically-driven topological and architectural alterations via restriction endonuclease (RE) reactions. We show that these systems display time-dependent rheological properties that depend on the concentrations and prope…
Multiscale simulation methods have been developed based on the local stress sampling strategy and applied to three flow problems with different difficulty levels: (a) general flow problems of simple fluids, (b) parallel (one-dimensional) flow problems of polymeric liquids, and (c) general (two- or three-dimensional) flow problems of polymeric liquids. In our multiscale methods, the local stress of each fluid element is calculated directly by performing microscopic or mesoscopic simulations according to the local flow quantities instead of using any constitutive relations. For simple fluids (a)…
The flow and deformation of macromolecules is ubiquitous in nature and industry, and an understanding of this phenomenon at both macroscopic and microscopic length scales is of fundamental and practical importance. Here we present the formulation of a general mathematical framework, which could be used to extract, from scattering experiments, the molecular relaxation of deformed polymers. By combining and modestly extending several key conceptual ingredients in the literature, we show how the anisotropic single-chain structure factor can be decomposed by spherical harmonics and experimentally …
We perform a detailed theoretical study of the edge fracture instability, which commonly destabilises the fluid-air interface during strong shear flows of entangled polymeric fluids, leading to unreliable rheological measurements. By means of direct nonlinear simulations, we map out phase diagrams showing the degree of edge fracture in the plane of the surface tension of the fluid-air interface and the imposed shear rate, within the Giesekus and Johnson-Segalman models, for different values of the nonlinear constitutive parameters that determine the dependencies on shear rate of the shear and …
We study the necking of a filament of complex fluid or soft solid subject to uniaxial tensile stretching, under conditions of constant imposed stress and force, by means of linear stability analysis and nonlinear simulations. We demonstrate necking to be a flow instability that is an unavoidable consequence of the constitutive behaviour of essentially any viscoelastic material. We derive criteria for the onset of necking that can be reported in terms of characteristic signatures in the shapes of the experimentally measured material functions, and that should therefore apply universally to all …
