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.     

Boundary-driven colloidal crystallization in simple shear flow

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.     

On the hydrodynamic behavior of colloidal aggregates

The hydrodynamic radiusR _H and the radius of gyrationR _G are calculated for a model of a colloidal aggregate, which assumes a spherically symmetric density distribution of the colloidal particles as is the fractal dimension.Dedicated to K. Dransfeld on the occasion of his 60th birthday     

Dense colloidal suspensions under time-dependent shear

We consider the nonlinear rheology of dense colloidal suspensions under a time-dependent simple shear flow. Starting from the Smoluchowski equation for interacting Brownian particles advected by shearing (ignoring fluctuations in fluid velocity), we develop a formalism which enables the calculation of time-dependent, far-from-equilibrium averages. Taking shear stress as an example, we derive exactly a generalized Green-Kubo relation and an equation of motion for the transient density correlator, involving a three-time memory function. Mode coupling approximations give a closed constitutive equation yielding the time-dependent stress for arbitrary shear rate history. We solve this equation numerically for the special case of a hard sphere glass subject to step strain.     

Elasticity and critical bending moment of model colloidal aggregates

The bending mechanics of singly bonded colloidal aggregates are measured using laser tweezers. We find that the colloidal bonds are capable of supporting significant torques, providing a direct measurement of the tangential interactions between particles. A critical bending moment marks the limit of linear bending elasticity, past which small-scale rearrangements occur. These mechanical properties underlie the rheology and dynamics of colloidal gels formed by diffusion-limited cluster aggregation, and give critical insight into the contact interactions between Brownian particles.     

Crystal nucleation of colloidal suspensions under shear

We use Brownian dynamics simulations in combination with the umbrella sampling technique to study the effect of shear flow on homogeneous crystal nucleation. We find that a homogeneous shear rate leads to a significant suppression of the crystal nucleation rate and to an increase of the size of the critical nucleus. A simple, phenomenological extension of classical nucleation theory accounts for these observations. The orientation of the crystal nucleus is tilted with respect to the shear direction.     

Evolution of an ensemble of fractal aggregates in a colloidal system

A theoretical study is presented of primary-minimum aggregation of colloidal particles, which generally leads to the formation of ramified fractal clusters. The focus is placed on the cooperative effects due to competition between aggregates for particles moving freely in the colloidal suspension. An analysis shows that the competition leads to aggregate density distributions and aggregation kinetics governed by more complicated laws as compared to those established in previous numerical and analytical studies of single-cluster growth.     

Magnetooptical studies of aggregates of nanoparticles in colloidal solutions of magnetite

The birefringence in a colloidal solution of nanosized magnetite particles in kerosene exposed to constant, alternating, and pulsed magnetic fields is studied. Data on the birefringence kinetics in nonstationary magnetic fields is used to determine the hydrodynamic radius of particle aggregates in solutions. The permanent dipole moment of aggregates and the anisotropy of the magnetic susceptibility are calculated based on the data of magnetooptical experiments. It is shown that the induced dipole moment plays a significant role in an orientation of aggregates of magnetic nanoparticles under the effect of a field.     

Shape and scale dependent diffusivity of colloidal nanoclusters and aggregates

The diffusion of colloidal nanoparticles and nanomolecular aggregates, which plays an important role in various biophysical and physicochemical phenomena, is currently under intense study. Here, we examine the shape and size dependent diffusion of colloidal nano- particles, fused nanoclusters and nanoaggregates using a hybrid fluctuating lattice Boltzmann-Molecular Dynamics method. We use physically realistic parameters characteristic of an aqueous solution, with explicitly implemented microscopic no-slip and full-slip boundary conditions. Results from nanocolloids below 10?nm in radii demonstrate how the volume fraction of the hydrodynamic boundary layer influences diffusivities. Full-slip colloids are found to diffuse faster than no-slip particles. We also characterize the shape dependent anisotropy of the diffusion coefficients of nanoclusters through the Green-Kubo relation. Finally, we study the size dependence of the diffusion of nanoaggregates comprising N?≤?108 monomers and demonstrate that the diffusion coefficient approaches the continuum scaling limit of N^?1/3.     

Three-dimensional imaging of colloidal glasses under steady shear

Using fast confocal microscopy we image the three-dimensional dynamics of particles in a yielded hard-sphere colloidal glass under steady shear. The structural relaxation, observed in regions with uniform shear, is nearly isotropic but is distinctly different from that of quiescent metastable colloidal fluids. The inverse relaxation time tau(alpha)(-1) and diffusion constant D, as functions of the local shear rate gamma*, show marked shear thinning with tau(alpha)(-1) proportional to D proportional to gamma*(0.8) over more than two decades in gamma*. In contrast, the global rheology of the system displays Herschel-Bulkley behavior. We discuss the possible role of large scale shear localization and other mechanisms in generating this difference.     

Processes underlying the laser photochromic effect in colloidal plasmonic nanoparticle aggregates

We have studied the dynamic and static processes occurring in disordered multiparticle colloidal Ag aggregates with natural structure and affecting their plasmonic absorption spectra under pico-and nanosecond pulsed laser radiations, as well as the physical origin responsible for these processes. We have shown that depending on the duration of the laser pulse,the mechanisms of laser modification of such aggregates can be associated both with changes in the resonant properties of the particles due to their heating and melting(picosecond irradiation mode) and with the particle shifts in the resonant domains of the aggregates(nanosecond pulses) which depend on the wavelength, intensity, and polarization of the radiation.These mechanisms result in formation of a narrow dip in the plasmonic absorption spectrum of the aggregates near the laser radiation wavelength and affect the shape and position of the dip. The effect of polydispersity of nanoparticle aggregates on laser photochromic reaction has been studied.     

Rejuvenation and overaging in a colloidal glass under shear

We report the modifications of the microscopic dynamics of a colloidal glass submitted to shear. We use multispeckle diffusing wave spectroscopy to monitor the evolution of the spontaneous slow relaxation processes after the samples have been submitted to various straining. We show that high shear rejuvenates the system and accelerates its dynamics, whereas moderate shear over-ages the system. We analyze these phenomena within the frame of the Bouchaud's trap model.     

One- and two-component colloidal glasses under transient shear

In concentrated colloidal mixtures different caging mechanisms exist and result in different arrested states: repulsive, attractive and asymmetric glasses as well as gel-like states. We discuss their microscopic structure, dynamics and rheological response. Special attention is given to the non-linear mechanical behaviour, in particular the transient rheological response after shear is started. Steps in both, shear rate and shear stress (creep test), are considered. The macroscopic viscoelastic response is related to the microscopic structure and dynamics on the individual-particle level.     

Restructuring of plasmonic nanoparticle aggregates with arbitrary particle size distribution in pulsed laser fields

We have studied processes of interaction of pulsed laser radiation with resonant groups of plasmonic nanoparticles(resonant domains) in large colloidal nanoparticle aggregates having different interparticle gaps and particle size distributions.These processes are responsible for the origin of nonlinear optical effects and photochromic reactions in multiparticle aggregates.To describe photo-induced transformations in resonant domains and alterations in their absorption spectra remaining after the pulse action,we introduce the factor of spectral photomodification.Based on calculation of changes in thermodynamic,mechanical,and optical characteristics of the domains,the histograms of the spectrum photomodification factor have been obtained for various interparticle gaps,an average particle size,and the degree of polydispersity.Variations in spectra have been analyzed depending on the intensity of laser radiation and various combinations of size characteristics of domains.The obtained results can be used to predict manifestation of photochromic effects in composite materials containing different plasmonic nanoparticle aggregates in pulsed laser fields.     

Star polymers in shear flow

Linear and star polymers in solution are studied in the presence of shear flow. The solvent is described by a particle-based mesoscopic simulation technique, which accounts for hydrodynamic interactions. The scaling properties of the average gyration tensor, the orientation angle, and the rotation frequency are investigated for various arm lengths and arm numbers. With increasing functionality f, star polymers exhibit a crossover in their flow properties from those of linear polymers to a novel behavior, which resembles the tank-treading motion of elastic capsules.     

Three-dimensional shear in granular flow

The evolution of granular shear flow is investigated as a function of height in a split-bottom Couette cell. Using particle tracking, magnetic-resonance imaging, and large-scale simulations, we find a transition in the nature of the shear as a characteristic height H* is exceeded. Below H* there is a central stationary core; above H* we observe the onset of additional axial shear associated with torsional failure. Radial and axial shear profiles are qualitatively different: the radial extent is wide and increases with height, while the axial width remains narrow and fixed.