Nucleation of symmetric domains in the coupled leaflets of a bilayer.

We study the kinetics governing the attainment of inter-leaflet domain symmetry in a phase-separating amphiphilic bilayer. "Indirect" inter-leaflet coupling via hydrophobic mismatch can induce an instability towards a metastable pattern of locally asymmetric domains upon quenching from high temperature. This necessitates a nucleation step to form the conventional symmetric domains, which are favoured by a "direct" inter-leaflet coupling. We model the energetics for a symmetric domain to nucleate from the metastable state, and find that an interplay between hydrophobic mismatch and thickness stretching/compression causes the effective hydrophobic mismatch, and thus line tension, to depend on domain size. This leads to strong departure from classical nucleation theory. We speculate on implications for cell membrane rafts or clusters, whose size may be of similar magnitude to estimated critical radii for domain symmetry.

Two-dimensional perturbations in a scalar model for shear banding.

We present an analytical study of a toy model for shear banding, without normal stresses, which uses a piecewise linear approximation to the flow curve (shear stress as a function of shear rate). This model exhibits multiple stationary states, one of which is linearly stable against general two-dimensional perturbations. This is in contrast to analogous results for the Johnson-Segalman model, which includes normal stresses, and which has been reported to be linearly unstable for general two-dimensional perturbations. This strongly suggests that the linear instabilities found in the Johnson-Segalman can be attributed to normal stress effects.

Validation of the Jarzynski relation for a system with strong thermal coupling: an isothermal ideal gas model.

We revisit the paradigm of an ideal gas under isothermal conditions. A moving piston performs work on an ideal gas in a container that is strongly coupled to a heat reservoir. The thermal coupling is modeled by stochastic scattering at the boundaries. In contrast to recent studies of an adiabatic ideal gas with a piston [R.C. Lua and A.Y. Grosberg, J. Phys. Chem. B 109, 6805 (2005); I. Bena, Europhys. Lett. 71, 879 (2005)], the container and piston stay in contact with the heat bath during the work process. Under this condition the heat reservoir as well as the system depend on the work parameter lambda and microscopic reversibility is broken for a moving piston. Our model is thus not included in the class of systems for which the nonequilibrium work theorem has been derived rigorously either by Hamiltonian [C. Jarzynski, J. Stat. Mech. (2004) P09005] or stochastic methods [G.E. Crooks, J. Stat. Phys. 90, 1481 (1998)]. Nevertheless the validity of the nonequilibrium work theorem is confirmed both numerically for a wide range of parameter values and analytically in the limit of a very fast moving piston, i.e., in the far nonequilibrium regime.

Lipid organization and the morphology of solid-like domains in phase-separating binary lipid membranes.

In multi-component lipid membranes, phase separation can lead to the formation of domains. The morphology of fluid-like domains has been rationalized in terms of membrane elasticity and line tension. We show that the morphology of solid-like domains is governed by different physics, and instead reflects the molecular ordering of the lipids. An understanding of this link opens new possibilities for the rational design of patterned membranes.

Budding and domain shape transformations in mixed lipid films and bilayer membranes.

We study the stability and shapes of domains with spontaneous curvature in fluid films and membranes, embedded in a surrounding membrane with zero spontaneous curvature. These domains can result from the inclusion of an impurity in a fluid membrane or from phase separation within the membrane. We show that for small but finite line and surface tensions and for finite spontaneous curvatures, an equilibrium phase of protruding circular domains is obtained at low impurity concentrations. At higher concentrations, we predict a transition from circular domains, or caplets, to stripes. In both cases, we calculate the shapes of these domains within the Monge representation for the membrane shape. With increasing line tension, we show numerically that there is a budding transformation from stable protruding circular domains to spherical buds. We calculate the full phase diagram and demonstrate two triple points of, respectively, bud-flat-caplet and flat-stripe-caplet coexistence.

Kinetics of symmetry and asymmetry in a phase-separating bilayer membrane.

We simulate a phase-separating bilayer in which the leaflets experience a direct coupling favoring local compositional symmetry ("registered" bilayer phases), and an indirect coupling due to hydrophobic mismatch that favors strong local asymmetry ("antiregistered" bilayer phases). For wide ranges of overall leaflet compositions, multiple competing states are possible. For estimated physical parameters, a quenched bilayer may first evolve toward a metastable state more asymmetric than if the leaflets were uncorrelated; subsequently, it must nucleate to reach its equilibrium, more symmetric, state. These phase-transition kinetics exhibit characteristic signatures through which fundamental and opposing interleaflet interactions may be probed. We emphasize how bilayer phase diagrams with a separate axis for each leaflet can account for overall and local symmetry or asymmetry, and capture a range of observations in the experiment and simulation literature.

Perspectives on the viscoelasticity and flow behavior of entangled linear and branched polymers.

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, and alternative approaches are briefly discussed. Finally, intriguing experimental findings and controversial issues that merit consistent explanation, such as shear banding instabilities, multiple stress overshoots in transient simple shear and enhanced steady-state elongational viscosity in polymer solutions, are discussed, and future directions such as branch point dynamics and anisotropic monomeric friction are outlined.

Kinetics of the shear banding instability in startup flows.

Motivated by recent light scattering experiments on semidilute wormlike micelles, we study the early stages of the shear banding instability using the nonlocal Johnson-Segalman model with a "two-fluid" coupling of flow to micellar concentration. We perform a linear stability analysis for coupled fluctuations in shear rate gamma;, micellar strain W, and concentration phi about an initially homogeneous state. This resembles the Cahn-Hilliard (CH) analysis of fluid-fluid demixing (although we discuss important differences). First, assuming the initial state to lie on the intrinsic constitutive curve, we calculate the "spinodal" onset of instability in sweeps along this curve. We then consider start-up "quenches" into the unstable region. Here the instability in general occurs before the intrinsic constitutive curve can be attained, so we analyze the fluctuations with respect to the time-dependent start-up flow. We calculate the selected length and time scales at which inhomogeneity first emerges. When the coupling between flow and concentration is switched off, fluctuations in the "mechanical variables" gamma; and W are independent of those in phi, and are unstable when the intrinsic constitutive curve has negative slope; but no length scale is selected. Coupling to the concentration enhances this instability at short length scales, thereby selecting a length scale, consistent with the recent light scattering experiments. The spinodal region is then broadened by an extent that increases with proximity to an underlying (zero-shear) CH fluid-fluid (phi) demixing instability. Far from demixing, the broadening is slight and the instability is still mechanically dominated (by deltagamma; and deltaW) with only small deltaphi. Close to demixing, instability sets in at a very low shear rate, where it is dominated instead by deltaphi. In this way, the model captures a smooth crossover from shear banding instabilities that are perturbed by concentration coupling to demixing instabilities that are induced by shear.

Instability of myelin tubes under dehydration: deswelling of layered cylindrical structures.

We report experimental observations of an undulational instability of myelin figures. Motivated by this, we examine theoretically the deformation and possible instability of concentric, cylindrical, multilamellar membrane structures. Under conditions of osmotic stress (swelling or dehydration), we find a stable, deformed state in which the layer deformation is given by deltaR infinity r(square root[B(A)/(hB)]), where B(A) is the area compression modulus, B is the interlayer compression modulus, and h is the repeat distance of layers. Also, above a finite threshold of dehydration (or osmotic stress), we find that the system becomes unstable to undulations, first with a characteristic wavelength of order square root[xi(d)0], where xi is the standard smectic penetration depth and d0 is the thickness of dehydrated region.

Cell dynamics simulations of shear-induced alignment and defect annihilation in stripe patterns formed by block copolymers.

The effect of large amplitude oscillatory shear on two-dimensional stripe patterns formed by block copolymers was investigated using cell dynamics simulations. A global orientational order parameter S and a correlation function for stripe normals G(r-r(')) were used to characterize the degree of stripe orientation under shear. The kinetics of stripe alignment, quantified by S, at various shear and quench conditions were studied as a function of strain amplitude, shear frequency, and temperature. The mechanisms of shear alignment and defect annihilation were investigated. A critical shear condition for complete alignment of stripes along the shear direction was also identified.

Statistical mechanics far from equilibrium: prediction and test for a sheared system.

We report the application of a far-from-equilibrium statistical-mechanical theory to a nontrivial system with Newtonian interactions in continuous boundary-driven flow. By numerically time stepping the force-balance equations of a one-dimensional model fluid we measure occupancies and transition rates in simulation. The high-shear-rate simulation data reproduce the predicted invariant quantities, thus supporting the theory that a class of nonequilibrium steady states of matter, namely, sheared complex fluids, is amenable to statistical treatment from first principles.

Nonmonotonic models are not necessary to obtain shear banding phenomena in entangled polymer solutions.

Recent experiments on entangled polymer solutions may indicate a constitutive instability, and have led some to question the validity of existing constitutive models. We use a modern constitutive model, the Rolie-Poly model plus a solvent viscosity, and show that (i) this simple class of models captures instability, (ii) shear banding phenomena is observable for weakly stable fluids in flow geometries with sufficiently inhomogeneous total stress, and (iii) transient phenomena exhibit inhomogeneities similar to shear banding, even for weakly stable fluids.

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 nonlocal 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 a sufficiently small ratio of the interfacial width l to cell length L(x). The instability saturates in finite amplitude interfacial fluctuations. For decreasing l/L(x) these undergo a nonequilibrium transition from simple traveling interfacial waves with constant average wall stress, to periodically rippling waves with a periodic stress response. When multiple shear bands are present we find erratic interfacial dynamics and a stress response suggesting low dimensional chaos.

Vorticity banding during the lamellar-to-onion transition in a lyotropic surfactant solution in shear flow.

We report on the rheology of a lyotropic lamellar surfactant solution (SDS/dodecane/pentanol/ water), and identify a discontinuous transition between two shear thinning regimes which correspond to the low-stress lamellar phase and the more viscous shear-induced multilamellar vesicle, or "onion" phase. We study in detail the flow curve, stress as a function of shear rate, during the transition region, and present evidence that the region consists of a shear-banded phase where the material has macroscopically separated into bands of lamellae and onions stacked in the vorticity direction. We infer very slow and irregular transformations from lamellae to onions as the stress is increased through the two-phase region, and identify distinct events consistent with the nucleation of small fractions of onions that coexist with sheared lamellae.

Flow phase diagrams for concentration-coupled shear banding.

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 Sigma (or strain rate gamma) and concentration, calculated within the two-fluid, non-local Johnson-Segalman (d-JS-phi) model. We also give results for the macroscopic flow curves Sigma(gamma,phi) for a range of (average) concentrations phi. 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, dSigma/dgamma>0. As the concentration is reduced, the width of the coexistence regime diminishes and eventually terminates at a non-equilibrium critical point [Sigmac,phic,gammac]. We outline the way in which the flow phase diagram can be reconstructed from a family of such flow curves, Sigma(gamma,phi), measured for several different values of phi. This reconstruction could be used to check new measurements of concentration differences between the coexisting bands. Our d-JS-phi 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 xi for equilibrium concentration-fluctuations. We show that the phase diagrams (and so also the flow curves) depend on the ratio r congruent with l/xi, 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 xi) at the critical point.

The effect of shear flow on the Helfrich interaction in lyotropic lamellar systems.

We study the effect of shear flow on the entropic Helfrich interaction in lyotropic surfactant smectic fluids. Arguing that flow induces an effective anisotropic surface tension in bilayers due to a combination of intermonolayer friction, bilayer collisions and convection, we calculate the reduction in fluctuations and hence the renormalised change in effective compression modulus and steady-state layer spacing. We demonstrate that non-permeable or slowly permeating membranes can be susceptible to an undulatory instability of the Helfrich-Hurault type, and speculate that such an instability could be one source of a transition to multilamellar vesicles.

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.

Early stage kinetics in a unified model of shear-induced demixing and mechanical shear banding instabilities.

We present a unified model of shear-induced demixing and "mechanical" shear banding instabilities in polymeric and surfactant solutions, by combining a simple flow instability with a two-fluid approach to concentration fluctuations. Within this model, we calculate the "spinodal" limit of stability of initially homogeneous shear states to demixing/banding, and predict the selected length and time scales at which inhomogeneity first emerges after a shear start-up "quench" into the unstable region, finding qualitative agreement with experiment. Our analysis is the counterpart, for this driven phase transition, of the Cahn-Hilliard calculation for unsheared fluid-fluid demixing.

Phase separation of rigid-rod suspensions in shear flow.

We analyze the behavior of a suspension of rigid-rod-like particles in shear flow using a modified version of the Doi model, and construct diagrams for phase coexistence under conditions of constant imposed stress and constant imposed strain rate, among paranematic, flow-aligning nematic, and log-rolling nematic states. We calculate the effective constitutive relations that would be measured through the regime of phase separation into shear bands. We calculate phase coexistence by examining the stability of interfacial steady states and find a wide range of possible "phase" behaviors.