Long-chained surfactant solutions have found widespread use in the oil and gas industry due to a host of attractive properties. In this paper, we characterize one such commercially used viscoelastic surfactant that forms a wormlike micellar gel at room temperature and a viscoelastic solution at higher temperatures. We probe both states by conducting linear and nonlinear rheological tests and analyze their behaviour under the framework of micellar rheology. Our study outlines departure from behaviour exhibited by more conventional micellar systems and uncovers interesting dynamics like shear-induced fracture and possible shear-banding in these materials. In doing so we provide a detailed understanding of a novel class of wormlike micellar solutions
We present an experimental study of the motion of a solid sphere falling through a wormlike micellar fluid. While smaller or lighter spheres quickly reach a terminal velocity, larger or heavier spheres are found to oscillate in the direction of their falling motion. The onset of this instability correlates with a critical value of the velocity gradient scale $Γ_{c}\sim 1$ s$^{-1}$. We relate this condition to the known complex rheology of wormlike micellar fluids, and suggest that the unsteady motion of the sphere is caused by the formation and breaking of flow-induced structures.
Wormlike micelles are self-assemblies of polymer chains that can break and recombine reversibly. In this paper, we derive a thermodynamically consistent two species micro-macro model of wormlike micellar solutions by employing an energetic variational approach. The model incorporates a breakage and combination process of polymer chains into the classical micro-macro dumbbell model for polymeric fluids in a unified variational framework. We also study different maximum entropy closure approximations to the new model by "variation-then-closure" and "closure-then-variation" approaches. By imposin…
The flow of viscoelastic wormlike micellar solutions (WLMs) in porous media is encountered in many practical applications like enhanced oil recovery or groundwater remediation. To understand the flow dynamics of these complex fluids in porous media, a model porous media consisting of a straight microchannel with micropore throats present in it, is very often used. In this study, we perform an extensive numerical investigation to understand the flow dynamics of wormlike micellar solutions based on the two-species Vasquez-Cook-McKinley (VCM) model for micelles through such model porous media. We…
The extensive application of surfactants motivates comprehensive and predictive theoretical studies that improve our understanding of the behaviour of these complex systems. In this study, an expression for the elastic free-energy density of a wormlike micellar chain is derived taking into account interactions between its constituent molecules. The resulting expression incorporates the sum of a quadratic term in the curvature and a quadratic term in the torsion of the centerline of wormlike micelle and thus resembles free-energy density functions for polymer chains and DNA available in the lit…
In the absence of inertia, a reciprocal swimmer achieves no net motion in a viscous Newtonian fluid. Here, we investigate the ability of a reciprocally actuated particle to translate through a complex fluid that possesses a network using tracking methods and birefringence imaging. A geometrically polar particle, a rod with a bead on one end, is reciprocally rotated using magnetic fields. The particle is immersed in a wormlike micellar (WLM) solution that is known to be susceptible to the formation of shear bands and other localized structures due to shear-induced remodeling of its microstructu…
In this work, we use flow visualization and rheometry techniques to study the dynamics and evolution of secondary flows in a model wormlike micellar solution sheared between concentric cylinders, i.e., in a Taylor-Couette (TC) cell. The wormlike micellar solution studied in this work contains cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal). This system can be shear banding and highly elastic, non-shear banding and moderately elastic, or nearly Newtonian as the temperature is varied over a narrow range. The effect of elasticity on transitions and instabilities is probed by c…
A mean-field kinetic model suggests that the relaxation dynamics of wormlike micellar networks is a long and complex process due to the problem of reducing the number of free end-caps (or dangling ends) while also reaching an equilibrium level of branching after an earlier overgrowth. The model is validated against mesoscopic molecular dynamics simulations and is based on kinetic equations accounting for scission and synthesis processes of blobs of surfactants. A long relaxation time scale is reached both with thermal quenches and small perturbations of the system. The scaling of this relaxati…
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.…
Beyond binary scission: a generalized three-species cascade breakage model for wormlike micellar solutions
School of Mathematics, Jilin University（吉林大学数学学院）；AI for Science and Engineering Center, Shenzhen Loop Area Institute（深圳_loop_区域研究院科学与工程人工智能中心）；Department of Mathematics, Texas State University（德克萨斯州立大学数学系）
The weakly nonlinear rheology of a surfactant solution of wormlike micelles is investigated from both a modeling and experimental perspective using the framework of medium amplitude parallel superposition (MAPS) rheology. MAPS rheology defines material functions, such as the third order complex compliance, which span the entire weakly nonlinear response space of viscoelastic materials to simple shear deformations. Three-tone oscillatory shear deformations are applied to obtain feature-rich data characterizing the third order complex compliance with high data throughput. Here, data for a CPyCl …
Linking molecular timescales to linear viscoelastic response in dilute and semidilute unentangled wormlike micelle solutions
IITB-Monash Research Academy（IITB-蒙纳士研究学院）；Department of Chemical Engineering, Indian Institute of Technology Bombay（印度理工学院孟买分校化学工程系）；Department of Chemical and Biological Engineering, Monash University（蒙纳士大学化学与生物工程系）；School of Chemistry, Monash University（蒙纳士大学化学学院）
Using Monte Carlo simulations, we investigate the self-assembly of model nanoparticles inside a matrix of model equilibrium polymers (or matrix of Wormlike micelles) as a function of the polymeric matrix density and the excluded volume parameter between polymers and nanoparticles. In this paper, we show morphological transitions in the system architecture via synergistic self-assembly of nanoparticles and the equilibrium polymers. In a synergistic self-assembly, the resulting morphology of the system is a result of the interaction between both nanoparticles and the polymers, unlike the polymer…
Diffusion studies using nuclear magnetic resonance (NMR) spectroscopy were conducted on two model surfactant solutions of cetyltrimethylammonium bromide/sodium salicylate (CTAB/NaSal) and cetylpyridinium chloride/sodium salicylate (CPCl/NaSal). By increasing the salt-to-surfactant concentration ratio, these systems display two peaks in the zero-shear viscosity and relaxation time, which are indicative of transitions from linear to branched micellar networks. The goal of this work is to assess the sensitivity of NMR diffusometry to different types of micellar microstructures and identify the me…
We investigate the effects of micellar entanglement number on the kinetics of shear banding flow formation in a Taylor-Couette flow. Three sets of wormlike micellar solutions, each set with a similar fluid elasticity and zero-shear-rate viscosity, but with varying entanglement densities, are studied under start-up of steady shear. Our experiments indicate that in the set with the low fluid elasticity, the transient shear banding flow is characterized by the formation of a transient flow reversal in a range of entanglement densities. Outside of this range, the transient flow reversal is not obs…
We review the experimental and theoretical results obtained during the past decade on the structure and rheology of wormlike micellar solutions. We focus on the linear and nonlinear viscoelasticity and emphasize the analogies with polymers. Based on a comprehensive survey of surfactant systems, the present study shows the existence of standard rheological behaviors for semidilute and concentrated solutions. One feature of this behavior is a shear banding transition associated with a stress plateau in the nonlinear mechanical response. For concentrated solutions, we show that in the plateau reg…
Surfactants in aqueous solutions self-assemble in the presence of salt, to form long, flexible worm-like micelles (WLM). WLM solutions exhibit viscoelastic properties and are used in many applications, such as for cosmetic products, drag reduction and hydraulic fracturing. The dynamics of bubbles in WLM solutions are important considerations for the stability of many of these products. In this manuscript, we investigate the thin film drainage dynamics leading up to the coalescence of bubbles in WLM solutions. The salts and surfactant type and concentrations were chosen so as to have the viscoe…
We report on the Rayleigh-Plateau instability in films of giant micelles solutions coating a vertical fibre. We observe that the dynamics of thin films coating the fibre could be very different from the Newtonian or standard Non-Newtonian cases. By varying the concentration of the components of the solutions and depending on the film thickness, we show for the first time that the Rayleigh-Plateau instability can be stabilized using surfactant solutions. Using global rheology and optical visualisations, we show that the development of shear-induced structures is required to stabilize the micell…
Many wormlike micellar systems exhibit appreciable shear thinning due to shear induced alignment. As the micelles get aligned introducing directionality in the system, the viscoelastic properties are no longer expected to be isotropic. An optical tweezers based active microrheology technique enables us to probe the out-of-equilibrium rheological properties of a wormlike micellar system simultaneously along two orthogonal directions - parallel to the applied shear, as well as perpendicular to it. While the displacements of a trapped bead - in response to active drag force carry signature of con…
Shearing of nanocomposites has shown to produce ordered nanostructures and orientation in the polymeric matrix. Due to the importance of the formation of an ordered structure of nanoparticles in a polymeric matrix to device wearable, flexible and photonic materials, its useful to get an insight of the shear-induced ordering and other properties of the polymeric nanocomposites. In this paper, we use a model Wormlike micellar matrix to study the arrangement and morphology of nanoparticles in the composite when the system is sheared using a hybrid multiparticle dynamics and molecular dynamics sim…
We study the early stages of the shear banding instability in semidilute wormlike micelles using the non-local Johnson-Segalman model with a two-fluid coupling of the concentration (phi) to the shear rate (gamma_dot) and micellar strain (tensor{W}). We calculate the ``spinodal'' limit of stability for sweeps along the homogeneous intrinsic flow curve. For startup ``quenches'' into the unstable region, the instability in general occurs before the homogeneous startup flow can attain the intrinsic flow curve. We predict the selected time and length scales at which inhomogeneity first emerges. In …
Hypotheses: A quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles of nonionic surfactants can be developed on the basis of a generalized model, which includes the classical 'phase separation' and 'mass action' models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: By analytical minimization of the free-energy functional we derived explicit expressions for the chain-extension and chain-end distribution functions in the hydrocarbon core of mixed micelles from t…
Hypotheses: The aggregation number and length of spherocylindrical (rodlike, wormlike) micelles in solutions of an ionic surfactant and salt can be predicted knowing the molecular parameters and the input concentrations of the species. This can be achieved by upgrading the quantitative molecular thermodynamic model from the previous parts of this series with an expression for the electrostatic component of micelle scission energy that is the excess free energy of the spherical endcaps with respect to the cylindrical part of the micelle. Theory: The thermodynamics of micellization is extended t…
Hypotheses: Quantitative molecular-thermodynamic theory of the growth of giant wormlike micelles in mixed nonionic surfactant solutions can be developed on the basis of a generalized model, which includes the classical phase separation and mass action models as special cases. The generalized model describes spherocylindrical micelles, which are simultaneously multicomponent and polydisperse in size. Theory: The model is based on explicit analytical expressions for the four components of the free energy of mixed nonionic micelles: interfacial-tension, headgroup-steric, chain-conformation compon…
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…
Complex fluids such as emulsions, colloidal gels, polymer or surfactant solutions are all characterized by the existence of a "microstructure" which may couple to an external flow on timescales that are easily probed in experiments. Such a coupling between flow and microstructure usually leads to instabilities under relatively weak shear flows that correspond to vanishingly small Reynolds numbers. Wormlike micellar surfactant solutions appear as model systems to study two examples of such instabilities, namely shear banding and elastic instabilities. Focusing on a semidilute sample we show tha…
Being able to reduce the size of a rheometer down to the micron scale is a unique opportunity to explore the mechanical response of expensive and/or confined liquids and gels. To this aim, we synthesize micron size wires with magnetic properties and examine the possibility of using them as microrheology probes. In this work, we exploit the technique of rotational magnetic spectroscopy by placing a wire in a rotating magnetic field and monitor its temporal evolution by time-lapse microscopy. The wire-based microrheology technique is tested on wormlike micellar surfactant solutions showing very …
Motivated by experiments on wormlike micelles, we study the early stages of the shear banding instability using a two-fluid Johnson-Segalman model. We perform a linear stability analysis for coupled fluctuations in shear rate, micellar strain and concentration about an initially homogeneous state. First we calculate the ``spinodal'' onset of instability in sweeps along the intrinsic constitutive curve. For startup ``quenches'' into the unstable region, the instability usually occurs before the intrinsic constitutive curve can be attained so we analyse the fluctuations with respect to the homog…
