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Using coarse-grained molecular dynamics simulations and an umbrella sampling method that uses local surfactant density as a reaction coordinate, we directly calculate, for the first time, both the scission and branching free energies of a model charged micelle [cationic cetyltrimethylammonium chloride (CTAC)] in the presence of inorganic and organic salts (hydrotropes). We find that while inorganic salt only weakly affects the micelle scission energy, organic hydrotropes produce a strong, nonmonotonic dependence of both scission energy and branching on salt concentration. The nonmonotonicity in scission energy is traced to a competition between electrostatic screening of the repulsions among the surfactant head groups and thinning of the micellar core, which result from attachment of the hydrotropes to the micelle surface. We are able to correlate the nonmonotonicity in the scission energy of CTAC micelles with the peak observed experimentally in viscosity versus hydrotrope concentration and the location of this peak in CTAC solutions. [ABSTRACT FROM AUTHOR]

We demonstrate through Brownian dynamics simulations a phase transition in plastic crystalline assemblies of Janus spheres through controlled pressure anisotropy. When the pressure in plane with hexagonally ordered layers is increased relative to that normal to the layers, a rapid first-order rotator-to-lamellar transition of Janus sphere orientation occurs at constant temperature. We show that the underlying mechanism closely follows the Maier-Saupe theory, originally developed for isotropic-to-nematic transition in positionally disordered materials but here applied to positionally ordered ones. Since the transition involves almost no translational diffusion or volume change, and occurs rapidly by particle rotation, the results should help guide the design of rapidly switchable colloidal crystals. [ABSTRACT FROM AUTHOR]

To assess the role of particle roughness in the rheological phenomena of concentrated colloidal suspensions, we develop model colloids with varying surface roughness length scales up to 10% of the particle radius. Increasing surface roughness shifts the onset of both shear thickening and dilatancy towards lower volume fractions and critical stresses. Experimental data are supported by computer simulations of spherical colloids with adjustable friction coefficients, demonstrating that a reduction in the onset stress of thickening and a sign change in the first normal stresses occur when friction competes with lubrication. In the quasi-Newtonian flow regime, roughness increases the effective packing fraction of colloids. As the shear stress increases and suspensions of rough colloids approach jamming, the first normal stresses switch signs and the critical force required to generate contacts is drastically reduced. This is likely a signature of the lubrication films giving way to roughness-induced tangential interactions that bring about load-bearing contacts in the compression axis of flow. [ABSTRACT FROM AUTHOR]

Using confocal microscopy, we directly observe that simple shear flow induces transient crystallization of colloids by wall-normal propagation of crystallization fronts from each shearing surface. The initial rate of the front propagation was 1.75±0.07 colloidal layers per unit of applied strain. The rate slowed to 0.29±0.04 colloidal layers per unit of applied strain as the two fronts approached each other at the midplane. The retardation of the front propagation is caused by self-concentration of shear strain in the growing bands of the lower-viscosity crystal, an effect that leads to a progressive reduction of the shear rate in the remaining amorphous material. These findings differ significantly from previous hypotheses for flow-induced colloidal crystallization by homogeneous mechanisms.

We report that an achiral particle with anisotropic rigidity can migrate in the vorticity direction in shear flow. A minimal "tetrumbbell" model of such a particle is constructed from four beads and six springs to make a tetrahedral structure. A combination of two different spring constants corresponding to "hard" and "soft" springs yields ten distinguishable tetrumbbells, which when simulated in shear flow with hydrodynamic interactions between beads but no Brownian motion at zero Reynolds number, produces five different types of behavior in which seven out of ten tetrumbbell structures migrate in the vorticity direction due to shear-induced chirality. Some of the structures migrate in the same direction along the vorticity direction even when the shear flow is reversed, which is impossible for permanently chiral objects.

We show that spin coating, an unsteady, nonuniform shear flow, produces spatiotemporal variation in the crystal order of concentrated colloidal dispersions that is a universal function of the local reduced critical stress and the macroscopic strain. The dependence of the crystal quality of model poly(methyl methacrylate) colloids on radial and axial position, spin speed, and particle size is quantified by confocal microscopy. The coupling of flow-induced crystallization with the centrifugally driven spin coating flow determines local crystal quality without a priori knowledge of the suspension rheology.

We report that a polymer molecule can be trapped spatially and conformationally using a microflow that has at least two stagnation points (or two points with equal velocity) and a net flow orthogonal to the line connecting them. Examples include a Taylor vortex flow and an electro-osmotic flow in a channel with surfaces that have a sinusoidal charge. Simulating the motion of a polymer molecule in these flows using Brownian dynamics, we find that such flows produce a curved polymer conformation, leading to an elastic force that drives migration against the flow, thus stabilizing this conformation. Simulations with hydrodynamic interactions confirm these predictions and show that there exists a repulsive interaction between two trapped polymers.

We perform atomistic and mesoscale simulations to explain the origin of experimentally observed stripelike patterns formed by immiscible ligands coadsorbed on the surfaces of gold and silver nanoparticles. We show that when the conformational entropy gained via this morphology is sufficient, microphase-separated stripelike patterns form. When the entropic gain is not sufficient, we instead predict bulk phase-separated Janus particles. We also show corroborating experimental results that confirm our simulational predictions that stripes form on flat surfaces as well as on curved nanoparticle surfaces.

Using a retarded-motion expansion to describe the polymer stress, we derive a low-dimensional model to understand the effects of polymer elasticity on the self-sustaining process that maintains the coherent wavy streamwise vortical structures underlying wall-bounded turbulence. Our analysis shows that at small Weissenberg numbers, Wi, elasticity enhances the coherent structures. At higher Wi, however, polymer stresses suppress the streamwise vortices (rolls) by calming down the instability of the streaks that regenerates the rolls. We show that this behavior can be attributed to the nonmonotonic dependence of the biaxial extensional viscosity on Wi, and identify it as the key rheological property controlling drag reduction.

When a chain, tethered at one end, is immersed in a fixed entanglement network, the mobile tip of the chain encounters an entropic potential barrier that penalizes deep fluctuations needed to bring the tip close to the tethering point. Using the tube model, Doi and Kuzuu [J. Polym. Sci., Polym. Lett. Ed. 18, 775 (1980)] estimated that this potential, which is crucial to describe the rheology of branched polymers in fixed networks and melts, has a quadratic form with a prefactor nu = 1.5. Later calculations based on regular lattices indicated that the potential is nonquadratic, and its steepness depends on the lattice coordination number. In this Letter, we analyze the primitive paths obtained using the bond-fluctuation model for chains with up to 12.5 entanglements. Our simulations confirm a quadratic form for the potential with a prefactor close to the Doi-Kuzuu value, nu approximately 1.5.