[Show abstract][Hide abstract] ABSTRACT: Flow-induced instabilities that lead to non-uniform stationary flow profiles have been observed in many different soft-matter systems. Two types of instabilities that lead to banded stationary states have been identified, which are commonly referred to as gradient- and vorticity-banding. The molecular origin of these instabilities is reasonably well understood. A third type of instability that has been proposed phenomenologically [Europhys. Lett., 1986, 2, 129 and Phys. Rev. E, 1995, 52, 4009] is largely unexplored. Essential to this “Shear-gradient Concentration Coupling” (SCC-) instability is a mass flux that is induced by spatial gradients of the shear rate. A possible reason that this instability has essentially been ignored is that the molecular origin of the postulated mass flux is not clear, and no explicit expressions for the shear-rate and concentration dependence of the corresponding transport coefficient exist. It is therefore not yet known what types of flow velocity- and concentration-profiles this instability gives rise to. In this paper, an expression for the transport coefficient corresponding to the shear-gradient induced mass flux is derived in terms of the shear-rate dependent pair-correlation function, and Brownian dynamics simulations for hard-spheres are presented that specify the shear-rate and concentration dependence of the pair-correlation function. This allows to explicitly formulate the coupled advection–diffusion equation and an equation of motion for the suspension flow velocity. The inclusion of a non-local contribution to the stress turns out to be essential to describe the SCC-banding transition. The coupled equations of motion are solved numerically, and flow- and concentration-profiles are discussed. It is shown that the SCC-instability occurs within the glass state at sufficiently small shear rates, leading to a banded flow-profile where one of the bands is non-flowing.
[Show abstract][Hide abstract] ABSTRACT: In this article we extend recent experimental developments [Rogers et al., Phys. Rev. Lett., 2012, 109, 098305] by providing a suitable theoretical framework for the derivation of exact expressions for the first cumulant (initial decay rate) of the correlation function measured in Evanescent Wave Dynamic Light Scattering (EWDLS) experiments. We focus on a dilute suspension of optically anisotropic spherical Brownian particles diffusing near a planar hard wall. In such a system, translational and rotational diffusion are hindered by hydrodynamic interactions with the boundary which reflects the flow incident upon it, affecting the motion of colloids. The validity of the approximation by the first cumulant for moderate times is assessed by juxtaposition to Brownian dynamics simulations, and compared with experimental results. The presented method for the analysis of experimental data allows the determination of penetration-depth-averaged rotational diffusion coefficients of spherical colloids at low density.
[Show abstract][Hide abstract] ABSTRACT: The response of concentrated dispersions of charged colloids to low-frequency electric fields is governed by field-induced inter-colloidal interactions resulting from the polarization of electric double layers and the layer of condensed ions, association and dissociation of condensed ions, as well as hydrodynamic interactions through field-induced electro-osmotic flow. The phases and states that can be formed by such field-induced interactions are an essentially unexplored field of research. Experiments on concentrated suspensions of rod-like colloids (fd-virus particles), within the isotropic-nematic phase coexistence region, showed that a number of phases/states are induced, depending on the field amplitude and frequency [Soft Matter, 2010, 6, 273]. In particular, a dynamical state is found where nematic domains form and melt on a time scale of the order of seconds. We discuss the microscopic origin of this dynamical state, which is attributed to the cyclic, electric-field induced dissociation and association of condensed ions. A semi-quantitative theory is presented for the dynamics of melting and formation of nematic domains, including a model for the field-induced dissociation/association of condensed ions. The resulting equation of motion for the orientational order parameter is solved numerically for parameters complying with the fd-virus system. A limit-cycle is found, with a cycling-time that diverges at the transition line in the field-amplitude versus frequency plane where the dynamical state first appears, in accord with experimental findings.
[Show abstract][Hide abstract] ABSTRACT: We review the effect of shear flow on the phase behavior and structure
of colloidal dispersions with increasing degree of complexity. We
discuss dispersions of colloidal rods, stiff living polymers like
wormlike micelles, and colloidal platelets. In addition, a review is
presented on sheared binary dispersions. For all cases we discuss the
interplay between thermodynamic instabilities and hydrodynamic
The European Physical Journal Special Topics 11/2013; 222(11):2739-2755. · 1.80 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The purpose of this study was to validate a new method to investigate the polymerization shrinkage vectors of composite during light curing and to evaluate the overall utility and significance of the technique.
An optical instrument was developed to measure the location and direction of the polymerization shrinkage strain vectors of dental composite during light curing using a particle tracking method with computer vision. The measurement system consisted of a CCD color camera, a lens and a filter, and software for multi-particle tracking. A universal hybrid composite (Z250, 3M ESPE, St. Paul MN, USA) was molded into thin disk-shaped specimens (un-bonded and bonded) or filled into a cavity within a tooth slab (bonded). The composite surface was coated with fluorescent particles prior to light curing. The images of the fluorescent particles were stored at 2 frames/s for 10min, and the movements of the particles on the composite surface were tracked with computer vision during curing. The polymerization shrinkage strain vectors as a function of time and location were analyzed. The volume shrinkage of the composite was also measured for comparison.
The linear and volume shrinkage of the composite at 10min were 0.75 (0.12)% and 2.26 (0.18)%, respectively. The polymerization shrinkage vectors were directed toward the center of the specimen and were isotropic in all directions when the composite was allowed to shrinkage freely without bonding. In contrast, the shrinkage vectors were directed toward the bonding surface and were anisotropic when the composite was bonded to a fixed wall. The regional displacement vectors of composite in a tooth cavity were dependent on the location, depth and time.
The new instrument was able to measure the regional linear shrinkage strain vectors over an entire surface of a composite specimen as a function of time and location. Therefore, this instrument can be used to characterize the shrinkage behaviors for a wide range of commercial and experimental visible-light-cure materials in relation to the composition, boundary condition and cavity geometry.
Dental materials: official publication of the Academy of Dental Materials 10/2013; · 2.88 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Microemulsion-based synthesis of inorganic nanoparticles is a versatile method, where many parameters can be varied to control the properties of products. In this work, solely by modifying the morphology of nonionic reverse microemulsions from spheres to cylinders, while keeping the water-to-surfactant ratio (W/S), salt concentration, volume fraction of surfactants, and temperature constant, we successfully controlled the variation of the length of PbCO3 nanorods with the same diameter. Short nanorods formed in the spherical microemulsions, while long nanorods are produced in the cylindrical microemulsions. In addition, an amorphous-to-amorphous transformation from spherical nanoparticles to nanorods is observed and nanorods self-assemble into one-dimensional chains in the microemulsion solution.
[Show abstract][Hide abstract] ABSTRACT: There is an abundance of experiments and theories on the glass transition of colloidal systems consisting of spherical particles. Much less is known about possible glass transitions in suspensions of rod-like colloids. In this study we present observations of a glass transition in suspensions of very long and thin rod-like, highly charged colloids. We use as a model system fd-virus particles (a DNA strand covered with coat proteins) at low ionic strength, where thick electric double layers are present. Structural arrest as a result of particle-caging is observed by means of dynamic light scattering. The glass-transition concentration is found to be far above the isotropic–nematic coexistence region. The morphology of the system thus consists of nematic domains with different orientations. Below the glass-transition concentration the initial morphology with large shear-aligned domains breaks up into smaller domains, and equilibrates after typically 50–100 hours. We quantify the dynamics of the transitional and the equilibrated texture by means of image time-correlation. A sharp increase of relaxation times of image time-correlation functions is found at the glass-transition concentration. The texture dynamics thus freezes at the same concentration where structural arrest occurs. We also observe a flow instability, which sets in after very long waiting times (typically 200–300 hours), depending on the rod concentration, which affects the texture morphology.
[Show abstract][Hide abstract] ABSTRACT: Self-assembly of nanoparticles triggered by attractive depletion forces presents a versatile pathway to build nanostructural superlattices directly in solution. In this work, the synthesis of square-like lead chromate (PbCrO4) nanoplatelets is described and their assembly into well-defined stacks by introducing various types of micelles as depletion agents is studied. The kinetics of the reversible assembling process in solution is probed by light scattering and the depletion-induced self-assembly of the nanoplatelets is investigated by transmission electron microscopy. For nonionic surfactants, rod-like micelles are found to be more efficient to produce self-assembly than sphere-like micelles, in accordance with an increased depletion force. Adding ionic surfactants leads additionally to a segregation of PbCrO4 rod reaction-byproducts.
[Show abstract][Hide abstract] ABSTRACT: We recently observed glass-like transitions in suspensions of the
charged fibrous viruses (fd), which are very long (880 nm) and thin (7
nm), stiff, rod-like DNA macromolecules. These charged fibrous viruses
are used as a good model system for charged colloidal rods, since they
carry a large surface charge through dissociation of negatively charged
coat proteins. We report here on a glass transition that leads to the
structural arrest as well as freezing of a texture dynamics. For the
determination of glass transition concentration, we have performed,
separately, the dynamicimage time correlation spectroscopy for
texture-dynamics, and dynamic light scattering to probe the structure
arrest in particle-dynamics.
[Show abstract][Hide abstract] ABSTRACT: We report on the observation of a glass transition in suspensions of very long and thin, highly charged colloidal rods (fd-virus particles). Structural particle arrest is found to occur at a low ionic strength due to caging of the charged rods in the potential setup by their neighbors through long-ranged electrostatic interactions. The relaxation time of density fluctuations as probed by dynamic light scattering is found to diverge within a small concentration range. The rod concentration where structural particle arrest occurs is well within the full chiral-nematic state, far beyond the two-phase isotropic-nematic coexistence region. The morphology of the suspensions thus consists of nematic domains with various orientations. We quantify the dynamics of the resulting texture with image-time correlation spectroscopy. Interestingly, the decay times of image correlation functions are found to diverge in a discontinuous fashion at the same concentration of charged rods where structural particle arrest is observed. At the glass-transition concentration, we thus find both structural arrest and freezing of the texture dynamics.
[Show abstract][Hide abstract] ABSTRACT: 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.
[Show abstract][Hide abstract] ABSTRACT: There is currently no experimental technique available to probe spatially resolved rotational diffusion of nanoparticles in the vicinity of a wall. We present the first experimental study of rotational diffusion of small spherical colloids, using dynamic evanescent wave scattering. A setup is used where the wave vector components parallel and perpendicular to the wall can be varied independently, and an expression is derived for the first cumulant of the intensity correlation function in VH evanescent wave geometry for optically anisotropic spheres. The experimental results are in agreement with theoretical predictions that take particle-wall hydrodynamic interactions into account.
[Show abstract][Hide abstract] ABSTRACT: A new near-wall velocimetry technique is proposed, based on evanescent wave dynamic light scattering, which allows for the measurement of near-wall velocity profile (characterized by an apparent slip velocity and a shear rate) with a resolution of tens of nanometers. A full theoretical expression of the correlation function is derived for the case of linear flow with negligible Brownian motion. The technique is demonstrated for latex spheres dispersed in water-glycerol mixtures.
The European Physical Journal E 07/2012; 35(7):62. · 2.18 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In order to interpret measured intensity autocorrelation functions obtained in evanescent wave scattering, their initial decay rates have been analyzed recently [P. Holmqvist, J. K. G. Dhont, and P. R. Lang, Phys. Rev. E 74, 021402 (2006); B. Cichocki, E. Wajnryb, J. Blawzdziewicz, J. K. G. Dhont, and P. R. Lang, J. Chem. Phys. 132, 074704 (2010); J. W. Swan and J. F. Brady, ibid. 135, 014701 (2011)]. A theoretical analysis of the longer time dependence of evanescent wave autocorrelation functions, beyond the initial decay, is still lacking. In this paper we present such an analysis for very dilute suspensions of spherical colloids. We present simulation results, a comparison to cumulant expansions, and experiments. An efficient simulation method is developed which takes advantage of the particular mathematical structure of the time-evolution equation of the probability density function of the position coordinate of the colloidal sphere. The computer simulation results are compared with analytic, first and second order cumulant expansions. The only available analytical result for the full time dependence of evanescent wave autocorrelation functions [K. H. Lan, N. Ostrowsky, and D. Sornette, Phys. Rev. Lett. 57, 17 (1986)], that neglects hydrodynamic interactions between the colloidal spheres and the wall, is shown to be quite inaccurate. Experimental results are presented and compared to the simulations and cumulant expansions.
The Journal of Chemical Physics 05/2012; 136(20):204704. · 3.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Particle shape plays an important role in controlling the optical, magnetic, and mechanical properties of nanoparticle suspensions as well as nanocomposites. However, characterizing the size, shape, and the associated polydispersity of nanoparticles is not straightforward. Electron microscopy provides an accurate measurement of the geometric properties, but sample preparation can be laborious, and to obtain statistically relevant data many particles need to be analyzed separately. Moreover, when the particles are suspended in a fluid, it is important to measure their hydrodynamic properties, as they determine aspects such as diffusion and the rheological behavior of suspensions. Methods that evaluate the dynamics of nanoparticles such as light scattering and rheo-optical methods accurately provide these hydrodynamic properties, but do necessitate a sufficient optical response. In the present work, three different methods for characterizing nonspherical gold nanoparticles are critically compared, especially taking into account the complex optical response of these particles. The different methods are evaluated in terms of their versatility to asses size, shape, and polydispersity. Among these, the rheo-optical technique is shown to be the most reliable method to obtain hydrodynamic aspect ratio and polydispersity for nonspherical gold nanoparticles for two reasons. First, the use of the evolution of the orientation angle makes effects of polydispersity less important. Second, the use of an external flow field gives a mathematically more robust relation between particle motion and aspect ratio, especially for particles with relatively small aspect ratios.
[Show abstract][Hide abstract] ABSTRACT: In concentrated suspensions of charged colloids, interactions between colloids can be induced by an external electric field through the polarization of charge distributions (within the diffusive double layer and the layer of condensed ions) and/or electro-osmotic flow. In case of rod-like colloids, these field-induced inter-colloidal interactions have recently been shown to lead to anomalous orientation perpendicular to the external field, and to phase/state transitions and dynamical states, depending on the field amplitude and frequency of the external field. As a first step towards a (semi-) quantitative understanding of these phenomena, we present a linear-response analysis of the frequency-dependent polarization of the layer of condensed ions on a single, long and thin cylindrical colloid. The in-phase and out-phase response functions for the charge distribution and the electric potential are calculated for arbitrary orientation of the cylindrical colloid. The frequency-dependent degree of alignment, which is proportional to the electric-field-induced birefringence, is calculated as well, and compared to experiments on dilute fd virus suspensions.
The European Physical Journal E 04/2011; 34(4):1-19. · 2.18 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A semimicroscopic derivation is presented of equations of motion for the density and the flow velocity of concentrated systems of entangled polymers. The essential ingredient is the transient force that results from perturbations of overlapping polymers due to flow. A Smoluchowski equation is derived that includes these transient forces. From this, an equation of motion for the polymer number density is obtained, in which body forces couple the evolution of the polymer density to the local velocity field. Using a semimicroscopic Ansatz for the dynamics of the number of entanglements between overlapping polymers, and for the perturbations of the pair-correlation function due to flow, body forces are calculated for nonuniform systems where the density as well as the shear rate varies with position. Explicit expressions are derived for the shear viscosity and normal forces, as well as for nonlocal contributions to the body force, such as the shear-curvature viscosity. A contribution to the equation of motion for the density is found that describes mass transport due to spatial variation of the shear rate. The two coupled equations of motion for the density and flow velocity predict flow instabilities that will be discussed in more detail in a forthcoming publication.
The Journal of Chemical Physics 03/2011; 134(12):124901. · 3.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The electric-field-induced charge distribution and potential around a colloidal sphere and rod in salt solutions are analyzed. The resulting field-induced colloid-colloid interactions are calculated for specific orientations. The colloids are assumed to be uncharged (or very weakly charged), such that the deflection of ion fluxes by the cores of the colloids is the dominant polarization mechanism (which is referred to as volume-polarization). Explicit expressions are derived for the frequency-dependent charge distribution and the potential in case of a symmetric electrolyte. It is shown that colloid-colloid interactions due to the induced charge distributions can be much larger than the thermal energy, and are therefore sufficiently strong to give rise to electric-field-induced phase transitions. The present study is a first step towards a quantitative description of field-induced transitions for systems where volume-polarization is the dominant polarization mechanism.
The European Physical Journal E 10/2010; 33(1):51-68. · 2.18 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: There is increasing interest in the use of viruses as model systems for fundamental research and as templates for nanomaterials. In this work, the rodlike fd virus was subjected to chemical modifications targeting different solvent-exposed functional groups in order to tune its surface properties, especially reversing the surface charge from negative to positive. The carboxyl groups of fd were coupled with different kinds of organic amines by carbodiimide chemistry, resulting in modified viruses that are positively charged over a wide range of pH. Care was taken to minimize intervirus cross linking, which often occurs because of such modifications. The surface amino groups were also grafted with poly(ethylene glycol) (PEG) end-functionalized with an active succinimidyl ester in order to introduce a steric stabilization effect. By combining charge reversal with PEG grafting, a reversible attraction between positively and negatively charged PEG-grafted fd viruses could be realized, which was tuned by the ionic strength of the solution. In addition, a charge-reversed fd virus forms only a pure nematic phase in contrast to the cholesteric phase of the wild type. These modified viruses might be used as model systems in soft condensed matter physics, for example, in the study of polyelectrolyte complexes or lyotropic liquid-crystalline phase behavior.