Suzanne M. Fielding

Rheology of giant micelles

Giant micelles are elongated, polymer-like objects created by the self-assembly of amphiphilic molecules (such as detergents) in solution. Giant micelles are typically flexible, and can become highly entangled even at modest concentrations. The resulting viscoelastic solutions show fascinating flow behaviour (rheology) which we address theoretically in this article at two levels. First, we summarize advances in understanding linear viscoelastic spectra and steady-state nonlinear flows, based on microscopic constitutive models that combine the physics of polymer entanglement with the reversible kinetics of self-assembly. Such models were first introduced two decades ago, and since then have been shown to explain robustly several distinctive features of the rheology in the strongly entangled regime, including extreme shear thinning. We then turn to more complex rheological phenomena, particularly involving spatial heterogeneity, spontaneous oscillation, instability and chaos. Recent understanding of these complex flows is based largely on grossly simplified models which capture in outline just a few pertinent microscopic features, such as coupling between stresses and other order parameters such as concentration. The role of ‘structural memory’ (the dependence of structural parameters such as the micellar length distribution on the flow history) in explaining these highly nonlinear phenomena is addressed. Structural memory also plays an intriguing role in the little-understood shear thickening regime, which occurs in a concentration regime close to but below the onset of strong entanglement, and which is marked by a shear-induced transformation from an inviscid to a gelatinous state.

Flow phase diagrams for concentration-coupled shear banding.

Abstract:After surveying the experimental evidence for concentration coupling in the shear banding of wormlike micellar surfactant systems, we present flow phase diagrams spanned by shear stress Σ (or strain rate ) and concentration, calculated within the two-fluid, non-local Johnson-Segalman (d-JS-φ) model. We also give results for the macroscopic flow curves Σ(¯,¯φ) for a range of (average) concentrations ¯φ. For any concentration that is high enough to give shear banding, the flow curve shows the usual non-analytic kink at the onset of banding, followed by a coexistence “plateau” that slopes upwards, dΣ/d¯ > 0. As the concentration is reduced, the width of the coexistence regime diminishes and eventually terminates at a non-equilibrium critical point [Σc,¯φc,¯c]. We outline the way in which the flow phase diagram can be reconstructed from a family of such flow curves, Σ(¯,¯φ), measured for several different values of ¯φ. This reconstruction could be used to check new measurements of concentration differences between the coexisting bands. Our d-JS-φ model contains two different spatial gradient terms that describe the interface between the shear bands. The first is in the viscoelastic constitutive equation, with a characteristic (mesh) length l. The second is in the (generalised) Cahn-Hilliard equation, with the characteristic length ξ for equilibrium concentration-fluctuations. We show that the phase diagrams (and so also the flow curves) depend on the ratio r ≡ l /ξ, with loss of unique state selection at r = 0. We also give results for the full shear-banded profiles, and study the divergence of the interfacial width (relative to l and ξ) at the critical point.

Shearing active gels close to the isotropic-nematic transition

We study numerically the rheological properties of a slab of active gel close to the isotropic-nematic transition. The flow behavior shows a strong dependence on the sample size, boundary conditions, and on the bulk constitutive curve, which, on entering the nematic phase, acquires an activity-induced discontinuity at the origin. The precursor of this within the metastable isotropic phase for contractile systems (e.g., actomyosin gels) gives a viscosity divergence; its counterpart for extensile suspensions admits instead a shear-banded flow with zero apparent viscosity.

Spatiotemporal Oscillations and Rheochaos in a Simple Model of Shear Banding

We study a simple model of shear banding in which the flow-induced phase is destabilized by coupling between flow and microstructure (wormlike micellar length). By varying the strength of instability and the applied shear rate, we find a rich variety of oscillatory and chaotic shear banded flows. At low shear and weak instability, the induced phase pulsates next to one wall of the flow cell. For stronger instability, high shear pulses ricochet across the cell. At high shear we see oscillating bands on either side of central defects. We discuss our results in the context of recent experiments.

Observable Dependence of Fluctuation-Dissipation Relations and Effective Temperatures

We study the nonequilibrium fluctuation-dissipation theorem (FDT) in the glass phase of Bouchauds trap model. We incorporate an arbitrary observable m and obtain its correlation and response functions in closed form. A limiting nonequilibrium FDT plot is approached at long times for most choices of m. In contrast to standard mean field models, however, the shape of the plot depends nontrivially on the observable, and its slope varies continuously even though there is a single scaling of relaxation times with age. Nonequilibrium FDT plots can therefore not be used to define a meaningful effective temperature T(eff) in this model. Consequences for the wider applicability of an FDT-derived T(eff) are discussed.

Criteria for shear banding in time-dependent flows of complex fluids.

We study theoretically the onset of shear banding in the three most common time-dependent rheological protocols: step stress, finite strain ramp (a limit of which gives a step strain), and shear startup. By means of a linear stability analysis we provide a fluid-universal criterion for the onset of banding for each protocol, which 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 thus have the same highly general status, in these time-dependent flows, as the widely known criterion for banding in steady state (of negatively sloping shear stress vs shear rate). We illustrate them with simulations of the Rolie-Poly model of polymer flows, and the soft glassy rheology model of disordered soft solids.

Nonlinear dynamics of an interface between shear bands

We study numerically the nonlinear dynamics of a shear banding interface in two dimensional planar shear flow, within the non-local Johnson Segalman model. Consistent with a recent linear stability analysis, we find that an initially flat interface is unstable with respect to small undulations for sufficiently small ratio of the interfacial width

Transient shear banding in entangled polymers: A study using the Rolie-Poly model

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Linear instability of planar shear banded flow

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Vorticity structuring and velocity rolls triggered by gradient shear bands

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