Phase stability of colloidal mixtures of spheres and rods.

We determined the phase boundaries of aqueous mixtures containing colloidal rod-like fd-viruses and polystyrene spheres using diffusing-wave spectroscopy and compared the results with free volume theory predictions. Excluded volume interactions in mixtures of colloidal rods and spheres lead to mediated depletion interactions. The strength and range of this attractive interaction depend on the concentrations of the particles, the length L and diameter D of the rods, and the radius R of the spheres. At strong enough attraction, this depletion interaction leads to phase separation. We experimentally determined the rod and sphere concentrations where these phase transitions occur by systematically varying the size ratios L/R and D/R and the aspect ratio L/D. This was done by using spheres with different radii and modifying the effective diameter of the rods through either the ionic strength of the buffer or anchoring a polymeric brush to the surface of the rods. The observed phase transitions were from a binary fluid to a colloidal gas/liquid phase coexistence that occurred already at very low concentrations due to the depletion efficiency of highly anisotropic rods. The experimentally measured phase transitions were compared to phase boundaries obtained using free volume theory (FVT), a well established theory for calculating the phase behavior of colloidal particles mixed with depletants. We find good correspondence between the experimental phase transitions and the theoretical FVT model where the excluded volume of the rod-like depletants was explicitly accounted for in both the reservoir and the system.

Crystal-to-Crystal Transition of Ultrasoft Colloids under Shear.

Ultrasoft colloids typically do not spontaneously crystallize, but rather vitrify, at high concentrations. Combining in situ rheo-small-angle-neutron-scattering experiments and numerical simulations we show that shear facilitates crystallization of colloidal star polymers in the vicinity of their glass transition. With increasing shear rate well beyond rheological yielding, a transition is found from an initial bcc-dominated structure to an fcc-dominated one. This crystal-to-crystal transition is not accompanied by intermediate melting but occurs via a sudden reorganization of the crystal structure. Our results provide a new avenue to tailor colloidal crystallization and the crystal-to-crystal transition at the molecular level by coupling softness and shear.

Shear-banding in entangled xanthan solutions: tunable transition from sharp to broad shear-band interfaces.

We report on the smooth transition between gradient-banded velocity profiles with a sharp interface and curved velocity profiles, both resulting from strong shear-thinning dispersions of concentrated xanthan (a highly charged poly-saccharide). Pronounced shear-banded flow, where two extended shear-bands are separated by a relatively sharp interface, is observed in a limited range of shear rates, at very low ionic strength and at a high concentration, using heterodyne light scattering to measure spatially resolved velocity profiles. The width of the interface between the coexisting shear-bands broadens to span a sizable fraction of the gap of the shear cell, either by changing the shear rate, by lowering the concentration, or by increasing the ionic strength. The broadening results in a smooth transition to highly curved velocity profiles and is connected to a disappearing flow birefringence. Thus, these experiments show that the classic shear-banding instability can give rise to highly curved velocity profiles, due to the existence of broad interfaces between the bands, with an extent of the order or larger than the cell gap width. This observation may aid to resolve the ongoing dispute concerning shear-banding of highly entangled polymeric systems, suggesting that the curved velocity profiles that have been observed in the past are in fact shear-banded states with an unusually broad interface.

Publisher's Note: Effect of the salt-induced micellar microstructure on the nonlinear shear flow behavior of ionic cetylpyridinium chloride surfactant solutions [Phys. Rev. E 95, 032603 (2017)].

This corrects the article DOI: 10.1103/PhysRevE.95.032603.

Effect of the salt-induced micellar microstructure on the nonlinear shear flow behavior of ionic cetylpyridinium chloride surfactant solutions.

The shear flow dynamics of linear and branched wormlike micellar systems based on cetylpyridinium chloride and sodium salicylate in brine solution is investigated through rheometric and scattering techniques. In particular, the flow and the structural flow response are explored via velocimetry measurements and rheological and rheometric small-angle neutron scattering (SANS) experiments, respectively. Although all micellar solutions display a similar shear thinning behavior in the nonlinear regime, the experimental results show that shear banding sets in only when the micelle contour length L[over ¯] is sufficiently long, independent of the nature of the micellar connections (either linear or branched micelles). Using rheometric SANS, we observe that the shear banding systems both show very similar orientational ordering as a function of Weissenberg number, while the short branched micelles manifest an unexpected increase of ordering at very low Weissenberg numbers. This suggests the presence of an additional flow-induced relaxation process that is peculiar for branched systems.

Trains, tails and loops of partially adsorbed semi-flexible filaments.

Polymer adsorption is a fundamental problem in statistical mechanics that has direct relevance to diverse disciplines ranging from biological lubrication to stability of colloidal suspensions. We combine experiments with computer simulations to investigate depletion induced adsorption of semi-flexible polymers onto a hard-wall. Three dimensional filament configurations of partially adsorbed F-actin polymers are visualized with total internal reflection fluorescence microscopy. This information is used to determine the location of the adsorption/desorption transition and extract the statistics of trains, tails and loops of partially adsorbed filament configurations. In contrast to long flexible filaments which primarily desorb by the formation of loops, the desorption of stiff, finite-sized filaments is largely driven by fluctuating filament tails. Simulations quantitatively reproduce our experimental data and allow us to extract universal laws that explain scaling of the adsorption-desorption transition with relevant microscopic parameters. Our results demonstrate how the adhesion strength, filament stiffness, length, as well as the configurational space accessible to the desorbed filament can be used to design the characteristics of filament adsorption and thus engineer properties of composite biopolymeric materials.

Colloidal liquid crystals in rectangular confinement: theory and experiment.

We theoretically and experimentally study nematic liquid crystal equilibria within shallow rectangular wells. We model the wells within a two-dimensional Oseen-Frank framework, with strong tangent anchoring, and obtain explicit analytical expressions for the director fields and energies of the 'diagonal' and 'rotated' solutions reported in the literature. These expressions separate the leading-order defect energies from the bulk distortion energy for both families of solutions. The continuum Oseen-Frank study is complemented by a microscopic mean-field approach. We numerically minimize the mean-field functional, including the effects of weak anchoring, variable order and random initial conditions. In particular, these simulations suggest the existence of higher-energy metastable states with internal defects. We compare our theoretical results to experimental director profiles, obtained using two types of filamentous virus particles, wild-type fd-virus and a modified stiffer variant (Y21M), which display nematic ordering in rectangular chambers, as found by confocal scanning laser microscopy. We combine our analytical energy expressions with experimentally recorded frequencies of the different equilibrium states to obtain explicit estimates for the extrapolation length, defined to be the ratio of the nematic elastic constant to the anchoring coefficient, of the fd-virus.

Depletion induced clustering in mixtures of colloidal spheres and fd-virus.

We determined the phase boundary of an ideal rod-sphere mixture consisting of fd-virus, which is an established model system for mono-disperse colloidal rods, and density matched mono-disperse polystyrene beads employing diffuse wave spectroscopy. The low volume fraction of fd needed to induce a phase separation at relatively low ionic strength exemplifies the fact that slender rods are very effective depletion agents. Confocal microscopy showed that stable clusters are formed during phase separation. Relaxation after shear deformation of these clusters showed that the phase separation is gas-liquid-like and that the interfacial tension involved is very low as in colloid-polymer mixtures.

Confinement induced splay-to-bend transition of colloidal rods.

We study the nematic phase of rodlike f d-virus particles confined to channels with wedge-structured walls. Using laser scanning confocal microscopy we observe a splay-to-bend transition at the single particle level as a function of the wedge opening angle. Lattice Boltzmann simulations reveal the underlying origin of the transition and its dependence on nematic elasticity and wedge geometry. Our combined work provides a simple method to estimate the splay-to-bend elasticity ratios of the virus and offers a way to control the position of defects through the confining boundary conditions.

Nonlinear behavior of nematic platelet dispersions in shear flow.

Dispersions of platelets in the nematic phase are submitted to large amplitude oscillatory shear flow and probed by high temporal resolution small angle x-ray scattering. The response displays rich dynamic and structural behavior. Under small amplitude deformations we observe an elastic response, while structurally symmetry is broken: a preferential direction of deformation is selected which induces off-plane orientation of the platelets. We associate the elastic responses with the tilting director of the platelets towards the flow direction at all strain amplitudes. At large strain amplitudes there is a yielding transition between elastic and plastic deformation, accompanied by a flipping of the director. At intermediate strain amplitudes the director has a rich dynamic behavior, illustrating the complex motion of platelets in shear flow. These observations are confirmed by steady-shear flow reversal experiments, which underline the unique character of sheared nematic platelet dispersions.

Supersaturated dispersions of rodlike viruses with added attraction.

The kinetics of isotropic-nematic (I-N) and nematic-isotropic (N-I) phase transitions in dispersions of rodlike fd viruses are studied. Concentration quenches were applied using pressure jumps in combination with polarization microscopy, birefringence, and turbidity measurements. The full biphasic region could be accessed, resulting in the construction of an experimental analog of the bifurcation diagram. The N-I spinodal points for dispersions of rods with varying concentrations of depletion agent (dextran) were obtained from orientation quenches using cessation of shear flow in combination with small-angle light scattering. We found that the location of the N-I spinodal point is independent of the attraction, which was confirmed by theory. Surprisingly, the experiments showed that also the absolute induction time, the critical nucleus, and the growth rate are insensitive of the attraction if the concentration is scaled to the distance to the phase boundaries.

Structure and phase diagram of an adhesive colloidal dispersion under high pressure: a small angle neutron scattering, diffusing wave spectroscopy, and light scattering study.

We have applied small angle neutron scattering (SANS), diffusing wave spectroscopy (DWS), and dynamic light scattering (DLS) to investigate the phase diagram of a sterically stabilized colloidal system consisting of octadecyl grafted silica particles dispersed in toluene. This system is known to exhibit gas-liquid phase separation and percolation, depending on temperature T, pressure P, and concentration phi. We have determined by DLS the pressure dependence of the coexistence temperature and the spinodal temperature to be dP/dT=77 bar/K. The gel line or percolation limit was measured by DWS under high pressure using the condition that the system became nonergodic when crossing it and we determined the coexistence line at higher volume fractions from the DWS limit of turbid samples. From SANS measurements we determined the stickiness parameter tau(B)(P,T,phi) of the Baxter model, characterizing a polydisperse adhesive hard sphere, using a global fit routine on all curves in the homogenous regime at various temperatures, pressures, and concentrations. The phase coexistence and percolation line as predicted from tau(B)(P,T,phi) correspond with the determinations by DWS and were used to construct an experimental phase diagram for a polydisperse sticky hard sphere model system. A comparison with theory shows good agreement especially concerning the predictions for the percolation threshold. From the analysis of the forward scattering we find a critical scaling law for the susceptibility corresponding to mean field behavior. This finding is also supported by the critical scaling properties of the collective diffusion.

Structure and short-time dynamics in suspensions of charged silica spheres in the entire fluid regime.

We present an experimental study of short-time diffusion properties in fluidlike suspensions of monodisperse charge-stabilized silica spheres suspended in dimethylformamide. The static structure factor S(q), the short-time diffusion function D(q), and the hydrodynamic function H(q) have been probed by combining x-ray photon correlation spectroscopy experiments with static small-angle x-ray scattering. Our experiments cover the full liquid-state part of the phase diagram, including de-ionized systems right at the liquid-solid phase boundary. We show that the dynamic data can be consistently described by the renormalized density fluctuation expansion theory of Beenakker and Mazur over a wide range of concentrations and ionic strengths. In accordance with this theory and Stokesian dynamics computer simulations, the measured short-time properties cross over monotonically, with increasing salt content, from the bounding values of salt-free suspensions to those of neutral hard spheres. Moreover, we discuss an upper bound for the hydrodynamic function peak height of fluid systems based on the Hansen-Verlet freezing criterion.

Attractive colloidal rods in shear flow.

The effect of shear flow on the isotropic-nematic phase transition of attractive colloidal rods is investigated by a combination of simulations and experiments. The isotropic phase aligns with the flow, while the nematic phase undergoes a collective rotational motion which frustrates the merging of the coexisting regions. The location of binodals, spinodals, and the tumbling-to-aligning transition line in the shear-rate versus concentration plane are investigated. The phase diagrams in the shear-concentration plane for the various strengths of attractions can be mapped onto a master curve by appropriate scaling.

Shear banding and rheochaos in associative polymer networks.

We present experimental evidence of an instability in the shear flow of transient networks formed by telechelic associative polymers. Velocimetry experiments show the formation of shear bands, following a complex pattern upon increasing the overall shear rate. The chaotic nature of the stress response in transient flow is indicative of spatiotemporal fluctuations of the banded structure. This is supported by time-resolved velocimetry measurements.

Collective diffusion in charge-stabilized suspensions: concentration and salt effects.

The authors present a joint experimental-theoretical study of collective diffusion properties in aqueous suspensions of charge-stabilized fluorinated latex spheres. Small-angle x-ray scattering and x-ray photon correlation spectroscopy have been used to explore the concentration and ionic-strength dependence of the static and short-time dynamic properties including the hydrodynamic function H(q), the wave-number-dependent collective diffusion coefficient D(q), and the intermediate scattering function over the entire accessible range. They show that all experimental data can be quantitatively described and explained by means of a recently developed accelerated Stokesian dynamics simulation method, in combination with a modified hydrodynamic many-body theory. In particular, the behavior of H(q) for de-ionized and dense suspensions can be attributed to the influence of many-body hydrodynamics, without any need for postulating hydrodynamic screening to be present, as it was done in earlier work. Upper and lower boundaries are provided for the peak height of the hydrodynamic function and for the short-time self-diffusion coefficient over the entire range of added salt concentrations.

Vorticity banding in rodlike virus suspensions.

Vorticity banding under steady shear flow is observed in a suspension of semiflexible colloidal rods (fd virus particles) within a part of the paranematic-nematic biphasic region. Banding occurs uniformly throughout the cell gap within a shear-rate interval (.gamma-, .gamma+) , which depends on the fd concentration. For shear rates below the lower-border shear rate .gamma- only shear elongation of inhomogeneities, which are formed due to paranematic-nematic phase separation, is observed. Within a small region just above the upper-border shear rate .gamma+ , banding occurs heterogeneously. An essential difference in the kinetics of vorticity banding is observed, depending on the morphology of inhomogeneities formed during the initial stages of the paranematic-nematic phase separation. Particle tracking and polarization experiments indicate that the vorticity bands are in a weak rolling flow, superimposed on the applied shear flow. We propose a mechanism for the origin of the banding instability and the transient stability of the banded states. This mechanism is related to the normal stresses generated by inhomogeneities formed due to the underlying paranematic-nematic phase transition.

Multiple shear-banding transitions in a supramolecular polymer solution.

We report on the nonlinear rheology of a reversible supramolecular polymer based on hydrogen bonding. The coupling between the flow-induced chain alignment and breakage and recombination of bonds between monomers leads to a very unusual flow behavior. Measured velocity profiles indicate three different shear-banding regimes upon increasing shear rate, each with different characteristics. While the first of these regimes has features of a mechanical instability, the second shear-banding regime is related to a shear-induced phase separation and the appearance of birefringent textures. The shear-induced phase itself becomes unstable at very high shear rates, giving rise to a third banding regime.

Crystallization kinetics of colloidal spheres under stationary shear flow.

A systematic experimental study of dispersions of charged colloidal spheres is presented on the effect of steady shear flow on nucleation and crystal growth rates. In addition, the nonequilibrium phase diagram as it relates to the melting line is measured. Shear flow is found to strongly affect induction times, crystal growth rates, and the location of the melting line. The main findings are that (1) the crystal growth rate for a given concentration exhibits a maximum as a function of the shear rate; (2) contrary to the monotonic increase in the growth rate with increasing concentration in the absence of flow, a maximum of the crystal growth rate as a function of concentration is observed for sheared systems; and (3) the induction time for a given concentration exhibits a maximum as a function of the shear rate. These findings are partly explained on a qualitative level.