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

The European Physical Journal E - We study the effect of shear flow on the entropic Helfrich interaction in lyotropic surfactant smectic fluids. Arguing that flow induces an effective anisotropic...     

Oscillating viscosity in a lyotropic lamellar phase under shear flow

We report some time-dependent behavior of lyotropic lamellar phase under shear flow. At fixed stress, near a layering instability, the system presents an oscillating shear rate. We build up a new stress versus shear rate diagram that includes temporal behavior. This diagram is made of two distinct branches of stationary states which correspond, respectively, to disordered and ordered multilamellar vesicle phases. When increasing the shear stress, prior to the transition to the ordered structural state, sustained oscillations of the viscosity are recorded. They correspond to periodic structural change of the entire sample between a disordered and a ordered state of multilamellar vesicles.     

Observations of the collapse of dilute lyotropic lamellar phases under shear flow

Experimental evidence of the collapse of dilute lamellar phases due to shear flow is presented. Two systems are used: one composed of brine and an ionic surfactant, and another composed of water, a nonionic surfactant, and cosurfactant. We observe this transition for a range of lamellar spacings and brine salinity. The results are in reasonable agreement with recent theory in which the suppression of fluctuations by shear plays an important role.     

Shear-induced collapse in a lyotropic lamellar phase

An entropically stabilized cetylpyridinium chloride, hexanol, and heavy brine lyotropic lamellar phase subjected to shear flow has been observed here by small angle neutron scattering to undergo collapse of smectic order above a threshold shear rate. The results are compared with theories predicting that such a lamellar phase sheared above a critical rate should lose its stability by a loss of resistance to compression due to the suppression of membrane fluctuations.     

Universal properties of lamellar systems under weak shear

We have observed that different lamellar phases (thermotropic, lyotropic of surfactants or blockcopolymers) share the same rheological properties = A(T)σ^m, m = 1.67±0.1, independently of their chemical nature, in a range of shear rates , shear stresses σ, and temperatures T, where the flow is stationary. It is argued that the key phenomenon is the appearance of screw dislocations whose glide under an applied shear counterbalances plastically the applied vorticity, and stabilizes the layers, whose slip past each other is thus made more feasible. The theory, which makes use in other respects of the high-temperature creep model in solids, reproduces correctly the power law behavior and the values of A(T). Received 18 April 2001 and Received in final form 25 October 2001     

Rheological behaviour of polyoxometalate-doped lyotropic lamellar phases

We study the influence of nanoparticle doping on the lyotropic liquid crystalline phase of the industrial surfactant Brij30 ( C₁₂E₄ and water, doped with spherical polyoxometalate nanoparticles smaller than the characteristic dimensions of the host lamellar phase. We present viscometry and in situ rheology coupled with small-angle X-ray scattering data that show that, with increasing doping concentration, the nanoparticles act to decrease the shear viscosity of the lamellar phase, and that a shear-induced transition to a multilamellar vesicle “onion” phase is pushed to higher shear rates, and in some cases completely suppressed. X-ray data reveal that the nanoparticles remain encapsulated within the membranes of the vesicles, thus indicating a viable method for the fabrication of nanoparticle incorporating organic vesicles.     

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.     

Optical manipulation of defects in a lyotropic lamellar phase

Here we study the line defect in a hyperswollen lamellar phase of lyotropic liquid crystal by applying a laser trapping method. We have succeeded in directly measuring the tension of a single isolated line defect and the adhesion energy between two defects. We demonstrate a new possibility of intentional patterning of various defects by direct optical manipulation. Furthermore, local rheological measurements provide information on the membrane organization around a particle and also evidence suggesting that flow in a lamellar phase has a two-dimensional nature.     

Role of dislocation loops on the elastic constants of lyotropic lamellar phases

We study the role of dislocation loops defects on the elasticity of lamellar phases by investigating the variation of the lamellar elastic constants, ˉ and K, induced by the proliferation of these defects. We focus our interest on one particular lamellar phase made up of a mixture of C₁₂E₅ and DMPC in water, which is already well-characterised. This lamellar phase undergoes a second-order (or weakly first-order) lamellar-to-nematic phase transition at about 19^°C and dislocation loops are seen to proliferate within the lamellar structure when temperature is decreased below 30^°C. The values of both elastic constants of this given lamellar phase are measured as a function of temperature, approaching the lamellar-to-nematic transition, with the help of Quasi-Elastic Light Scattering (QELS) on oriented lamellar phases. Very surprisingly we observe a strong and rapid increase in both ˉ and K as the lamellar-to-nematic transition temperature is approached. These increases are seen to start as soon as dislocation loops can be observed in the lamellar phase. We interpret our results as being the consequence of the appearance and proliferation of dislocation loops within the lamellar structure. According to a simple model we developped we show that ˉ and K are proportional to the density of dislocation loops in the lamellar phase.     

Confined diffusion of hydrophilic probes inserted in lyotropic lamellar phases

The dynamic behaviour of three hydrophilic probes (two dyes and one fluorescently-labelled protein) inserted in the water layers of lyotropic lamellar phases has been studied by confocal fluorescence recovery experiments. Two different, ionic (AOT/NaCl/ H(2)O and non-ionic ( C(12)E(5) /hexanol/ H(2)O host systems were studied. The confinement effect has been carefully monitored using the swelling properties of the lamellar phases. In all cases, we measure the evolution of the probe diffusion coefficient in the layer plane D ( perpendicular) versus the separation between the membranes d(w). Depending on the composition of the lamellar phase, this distance can be continuously adjusted from 500A to about 20A. For all systems, we observe a first regime, called dilute regime, where the diffusion coefficient decreases almost linearly with 1/d (w) . In this regime, the Faxén theory for the friction coefficient of a spherical particle symmetrically dragged between two rigid walls can largely explain our results. More unexpectedly, when the membranes are non-ionic, and also quite flexible ( C(12)E(5) /hexanol in water), we observe the existence of a second, concentrated (or confined) regime, where the diffusion coefficient is nearly constant and different from zero for membrane separations smaller than the particle size. This new regime can be heuristically explained by simple arguments taking into account the membrane fluidity.     

Curvature walls and focal conic domains in a lyotropic lamellar phase

In the quasi-ternary CPCl/brine/hexanol lyotropic system, the interface of the lamellar and L₃ sponge phases displays a phenomenon of epitaxy: the layers of the lamellar phase tend to make a constant non-trivial angle with the interface. Thin samples of lamellar phase embedded in the sponge phase are thus submitted to oblique anchoring conditions and defects are created in the lamellar phase in order to satisfy the bulk lamellar ordering and the boundary conditions. We have studied small droplets of lamellar phase in the sponge phase. They do not exhibit the classic defects (focal conic domains) but wall defects, which appear in order to satisfy the smectic elasticity and the boundary conditions. Moreover we show through experiments in controlled geometry that, even in the presence of focal conic domains, wall defects control the size and periodicity of the textures which are observed at the interface. Received 4 November 1998     

Instability of a lamellar phase under shear flow: formation of multilamellar vesicles

The formation of closed-compact multilamellar vesicles (referred to in the literature as the "onion texture") obtained upon shearing lamellar phases is studied using small-angle light scattering and cross-polarized microscopy. By varying the shear rate gamma;, the gap cell D, and the smectic distance d, we show that: (i) the formation of this structure occurs homogeneously in the cell at a well-defined wave vector q(i), via a strain-controlled process, and (ii) the value of q(i) varies as (dgamma;/D)(1/3). These results strongly suggest that formation of multilamellar vesicles may be monitored by an undulation (buckling) instability of the membranes, as expected from theory.     

Quantitative analysis of lyotropic lamellar phases SANS patterns in powder oriented samples

We have developed a detailed numerical method based on the Caillé model to fit Small Angle Neutron Scattering profiles of powder-oriented lyotropic lamellar phases. We thus obtain quantitative values for the Caillé parameter and the smectic penetration length from which we can derive the smectic compression modulus and the membrane mean bending modulus. Our method, applied to a surfactant lamellar phase system decorated by amphiphilic copolymers, provides excellent fits for any intermembrane spacing or membrane concentration over the entire q-range of the SANS experiments. We compare our fits with those obtained from the model of Nallet et al. (J. Phys. II 3, 487 (1993)), which is reviewed. Good fits are obtained with both methods for samples exhibiting “hard” smectic order (sharp Bragg peak, moderate small angle scattering). Only our procedure, however, gives good fits in the case of “soft” smectic order (smooth Bragg peak, strong small angle scattering). A quantitative criterion to discriminate between these “soft” and “hard” samples is also proposed, based on a simple analogy with smectic-A liquid crystal in contact with an undulating solid surface. This allows us to anticipate the type of thermodynamic information that can be derived from the fits.     

The effect of magnetic fields and boundary conditions on the shear flow of nematics

The flow of a nematic liquid crystal between plane parallel plates, with one plate moving with uniform velocity relative to the other, is discussed. The apparent viscosity, orientation and velocity profiles are computed forp-azoxyanisole as functions of shear rate and magnetic field for symmetric and asymmetric molecular alignment at the plates. For symmetric homeotropic boundary condition, a magnetic field applied along the flow direction exhibits a threshold reminiscent of a Freedericksz transition in the hydrostatic case. In general the apparent viscosity for the asymmetric boundary condition is less than that for the symmetric case.     

Structure and rheology of the defect-gel states of pure and particle-dispersed lyotropic lamellar phases

We present important new results from light-microscopy and rheometry on a moderately concentrated lyotropic smectic, with and without particulate additives. Shear-treatment aligns the phase rapidly, except for a striking network of oily-streak defects, which anneals out much more slowly. If spherical particles several microns in diameter are dispersed in the lamellar medium, part of the defect network persists under shear-treatment, its nodes anchored on the particles. The sample as prepared has substantial storage and loss moduli, both of which decrease steadily under shear-treatment. Adding particles enhances the moduli and retards their decay under shear. The data for the frequency-dependent storage modulus after various durations of shear-treatment can be scaled to collapse onto a single curve. The elasticity and dissipation in these samples thus arises mainly from the defect network, not directly from the smectic elasticity and hydrodynamics. Received 19 April 1999 and Received in final form 20 May 1999