Colloidal glasses

Colloidal suspensions are important model systems for the study of phase transitions. The glass transition, especially, can be followed more directly with colloidal systems and compared to theoretical predictions. At high volume fractions of the colloidal particles the density fluctuations are partially frozen in. This can be identified by the typical plateau values in the time correlation function. If one compares the experimental results with the mode coupling theory, a very good agreement can be obtained. Currently, some new experimental results concerning the dynamical heterogeneity in colloidal systems are under discussion and will certainly initiate new theoretical developments.     

Viscosity of concentrated colloidal suspensions: comparison of bidisperse models

In this paper, recent advances in the study of rheological behavior of concentrated bimodal suspensions are briefly reviewed. The predictive models are divided into two categories, namely, the effective volume fraction (or hard sphere scaling) approach and the separation of contributions approach. Predictions of both approaches are compared with experimental data of electrostatically and sterically stabilized suspensions. It is shown that the predictions of both hard sphere scaling and the scaling method of Zaman and Moudgil (J. Colloid Interface Sci. 212 (1999) 167) to separate the contributions of fine and coarse particles are in good agreement with the experimentally observed results. The approach by Dames, Morrison, Wilenbacher (Rheol. Acta 40 (2001) 434) to separate the hard-sphere and non-hard-sphere contributions is investigated using the aqueous silica and polystyrene suspensions respectively. A good agreement is shown for aqueous silica suspensions. However, significant differences between the predictions and experimental data are found for the sterically stabilized polystyrene suspensions, suggesting a more generalized expression is needed. As an attempt to classify the models on the viscosity of colloidal suspensions, the present study will provide guidelines for interpretation of experimental results and for the development of more comprehensive predictive methodologies for polydispersed colloidal dispersions.     

Video microscopy of colloidal suspensions and colloidal crystals

Colloidal suspensions are simple model systems for the study of phase transitions. Video microscopy is capable of directly imaging the structure and dynamics of colloidal suspensions in different phases. Recent results related to crystallization, glasses, and 2D systems complement and extend previous theoretical and experimental studies. Moreover, new techniques allow the details of interactions between individual colloidal particles to be carefully measured. Understanding these details will be crucial for designing novel colloidal phases and new materials, and for manipulating colloidal suspensions for industrial uses.     

Dynamic effects on colloidal electric interactions

Dynamic behaviors are abundant in field-responsive colloidal suspensions. Being beyond the usual point-dipole approximation, we develop a multiple image method of dipoles for two dynamic unequal colloidal dielectric spherical particles, which can be perfectly reduced to those for two static conducting particles. The method is applied to investigate colloidal electric interparticle forces under various conditions of dynamics. As a result, we find that the force can be enhanced, reduced, or even changed from attraction to repulsion, or vice versa. Some other interesting results are also reported. Our theoretical results are compared favorably with existing experimental observations. Therefore, it becomes possible to achieve desired colloidal structures by adjusting colloidal interactions by choosing appropriate dynamic phenomena.     

Simulations of the PDF functions for dilute colloidal suspensions of molecular particles flowing in mesopores with rough surface boundaries

Simulations have been carried out to analyze the dynamics of dilute colloidal suspensions of macromolecular particles in solutions flowing in pores, subject to hydrodynamic forces, Brownian motion and stochastic collisions at rough pore boundaries in a two-dimensional spatial frame. A theoretical model is developed and intensively analyzed for the treatment of the mechanical restitution of the particles due to dynamic collisions at these boundaries. In particular we are able to calculate the Probability distribution functions for the spatial positions and the orientations of rod-like particles inside the pores. The results are presented for different widths of pore channels referenced to the size of a rod-like particle. These simulations are general in the sense that they are developed for confining and open pore channels, rough at the nano scale. The simulations also permit calculating the nematic order parameters for colloidal suspensions; the model calculation is applied for dilute colloidal suspensions of carbon nano-tubes in an aqueous single-stranded DNA solution flowing inside pores. Our calculated nematic order results for dilute suspensions of particles of known lengths flowing inside porous systems should indicate, when coupled to birefringence and dichroism experimental results, the possibility to estimate the pore widths for these systems.     

Charge and salt-driven reentrant order-disorder and gas-solid transitions in charged colloids

Monte Carlo simulations have been performed for aqueous charged colloidal suspensions as a function of effective charge density (sigma) on the particles and salt concentration C(s). We vary the effective charge density in our simulations over a range where a reentrant solid-liquid transition in suspensions of silica and polymer latex particles has been reported by Yamanaka et al. (Phys. Rev. Lett. 80 (1998) 5806). We show that at low ionic strengths a homogeneous liquid-like ordered suspension undergoes crystallization upon increasing sigma. Further increase in sigma resulted once again in a disordered state, which is in agreement with experimental observations. In addition to this reentrant order-disorder transition, we observe an inhomogeneous-to-homogeneous transition in our simulations when salt is added to the disordered inhomogeneous state. This inhomogeneous-to-homogeneous disordered transition is analogous to the solid-gas transition of atomic systems and has not yet been observed in charged colloids. The reported experimental observations on charged colloidal suspensions are discussed in the light of present simulation results.     

Dynamic Mobility of Colloidal Particles with Thick Double Layers

The dynamic mobility spectra of several colloidal systems having a ratio of particle radius to double-layer thickness between 1 and 20 have been measured using the technique of electroacoustics. Good agreement is found between the experimental mobility spectra and the theoretical spectra generated by the computer program of Manglesdorf and White for spherical monodisperse suspensions with sizes in the neighborhood of 0.1 μm. Smaller and larger particles show some minor discrepancies which are more likely to be due to limitations of the model systems being used for the test than to any basic limitation of the theoretical analysis. Copyright 2000 Academic Press.     

Long-range interactions between soft colloidal particles in slit-pore geometries

Combining theoretical and experimental techniques, we investigate the structure formation of charged colloidal suspensions of silica particles in bulk and in spatial confinement (slit-pore geometry). Our focus is to identify characteristic length scales determining typical quantities, such as the position of the main peak of the bulk structure factor and the period of the oscillatory force profile in the slitpore. We obtain these quantities from integral equations/SANS experiments (bulk) and Monte Carlo simulations/colloidal probe-AFM measurements (confinement), in which the theoretical calculations are based on the Derjaguin-Landau-Verwey-Overbeck (DLVO) potential. Both in bulk and in the slitpore, we find excellent qualitative and quantitative agreement between theory and experiment as long as the ionic strength chosen in the DLVO potential is sufficiently low (implying a relatively long-ranged interaction). In particular, the bulk properties of these systems obey the widely accepted density scaling of xi proportional to phi(-1/3). On the other hand, systems with larger ionic strengths and, consequently, more short-ranged interactions do not obey such power law behavior and rather resemble an uncharged hard-sphere fluid, in which the relevant length scale is the particle diameter.     

Electric double layer for spherical particles in salt-free concentrated suspensions including ion size effects

The equilibrium electric double layer (EDL) that surrounds colloidal particles is essential for the response of a suspension under a variety of static or alternating external fields. An ideal salt-free suspension is composed of charged colloidal particles and ionic countercharges released by the charging mechanism. Existing macroscopic theoretical models can be improved by incorporating different ionic effects usually neglected in previous mean-field approaches, which are based on the Poisson-Boltzmann equation (PB). The influence of the finite size of the ions seems to be quite promising because it has been shown to predict phenomena like charge reversal, which has been out of the scope of classical PB approximations. In this work we numerically obtain the surface electric potential and the counterion concentration profiles around a charged particle in a concentrated salt-free suspension corrected by the finite size of the counterions. The results show the high importance of such corrections for moderate to high particle charges at every particle volume fraction, especially when a region of closest approach of the counterions to the particle surface is considered. We conclude that finite ion size considerations are obeyed for the development of new theoretical models to study non-equilibrium properties in concentrated colloidal suspensions, particularly salt-free ones with small and highly charged particles.     

Re-entrant kinetic arrest and elasticity of concentrated suspensions of spherical and nonspherical repulsive and attractive colloids

We have designed and studied a new experimental colloidal system to probe how the weak shape anisotropy of uniaxial particles and variable repulsive (Coulombic) and attractive (van der Waals) forces influence slow dynamics, shear elasticity, and kinetic vitrification in dense suspensions. The introduction of shape anisotropy dramatically delays kinetic vitrification and reduces the shear elastic modulus of colloidal diatomics relative to their chemically identical spherical analogs. Tuning the interparticle interaction from repulsive, to nearly hard, to attractive by increasing suspension ionic strength reveals a nonmonotonic re-entrant dynamical phase behavior (glass-fluid-gel) and a rich variation of the shear modulus. The experimental results are quantitatively confronted with recent predictions of ideal mode coupling and activated barrier hopping theories of kinetic arrest and elasticity, and good agreement is generally found with a couple of exceptions. The systems created may have interesting materials science applications such as flowable ultrahigh volume fraction suspensions, or responsive fluids that can be reversibly switched between a flowing liquid and a solid nonequilibrium state based on in situ modification of suspension ionic strength.     

Optical absorbance of colloidal suspensions of silver polyhedral nanoparticles

The optical absorption of colloidal suspensions made of silver nanoparticles with polyhedral shapes is studied experimentally and theoretically. The influence of the shape on the optical response is investigated by comparing the measured absorbance with theoretical results for icosahedral, decahedral, and cuboctahedral silver nanoparticles. The theoretical spectra are obtained within the discrete dipole approximation. We find that colloidal suspensions of silver nanoparticles with a small dispersion of size distribution show very few structural shapes.     

dc Electrokinetics for spherical particles in salt-free concentrated suspensions including ion size effects

We study the electrophoretic mobility of spherical particles and the electrical conductivity in salt-free concentrated suspensions including finite ion size effects. An ideal salt-free suspension is composed of just charged colloidal particles and the added counterions that counterbalance their surface charge. In a very recent paper [Roa et al., Phys. Chem. Chem. Phys., 2011, 13, 3960-3968] we presented a model for the equilibrium electric double layer for this kind of suspensions considering the size of the counterions, and now we extend this work to analyze the response of the suspension under a static external electric field. The numerical results show the high importance of such corrections for moderate to high particle charges, especially when a region of closest approach of the counterions to the particle surface is considered. The present work sets the basis for further theoretical models with finite ion size corrections, concerning particularly the ac electrokinetics and rheology of such systems.     

Tracer diffusion in colloidal suspensions under dilute and crowded conditions with hydrodynamic interactions

We consider tracer diffusion in colloidal suspensions under solid loading conditions, where hydrodynamic interactions play an important role. To this end, we carry out computer simulations based on the hybrid stochastic rotation dynamics-molecular dynamics (SRD-MD) technique. Many details of the simulation method are discussed in detail. In particular, our choices for the SRD-MD parameters and for the different scales are adapted to simulating colloidal suspensions under realistic conditions. Our simulation data are compared with published theoretical, experimental and numerical results and compared to Brownian dynamics simulation data. We demonstrate that our SRD-MD simulations reproduce many features of the hydrodynamics in colloidal fluids under finite loading. In particular, finite-size effects and the diffusive behavior of colloids for a range of volume fractions of the suspension show that hydrodynamic interactions are correctly included within the SRD-MD technique.     

Rheological aspects of colloidal gels in thermoresponsive microgel suspensions: formation,structure, and linear and nonlinear viscoelasticity

This review focuses on the rheological aspects of colloidal gels that are a three-dimensional sparse network made of aggregated attractive particles formed in the aqueous suspensions of microgels composed of thermoresponsive polymers. Heating changes the dominant interparticle interactions from repulsive to attractive because of the hydrophilic-to-hydrophobic transition. Under appropriate conditions, the hydrophobic microgel suspensions form colloidal gels behave as a yield fluid. The elastic and yielding features of the colloidal gels are considerably different from those of the repulsive glass which is formed by the dense packing of the hydrophilic microgels at low temperatures. The thermoresponsive microgel suspensions undergoing colloidal gelation have attracted much attention from not only the academic interests but also the potentials as a functional suspension because they show interesting and marked changes in viscoelasticity when subjected to temperature variation. We discuss the criteria and dynamics of colloidal gelation, the structure, and linear and nonlinear viscoelasticity of the colloid gels with an emphasis on the results of the experimental studies.     

A broad frequency range dielectric spectrometer for colloidal suspensions: cell design, calibration, and validation

Electrode polarization complicates low-frequency measurements of the dielectric response of electrolyte solutions and colloidal suspensions. To deal with this longstanding problem, a new dielectric cell was developed along with a model based on the standard electrokinetic theory. The parallel plate cell utilizes a thin chamber that is easily filled and emptied; different chamber thicknesses are readily accommodated. The analytical form of the theoretical impedance model makes data analysis straightforward. Using standard electrolytes, the device and the theoretical model were tested over a wide range of frequencies for several electrolyte concentrations. Excellent agreement was found between the theory and the experimental data. The methodology developed to account for polarization effects exhibits a significant improvement over the conventional approaches and points up a deficiency in often-used equivalent circuit models.     

Weak correlations between local density and dynamics near the glass transition

We perform experiments on two different dense colloidal suspensions with confocal microscopy to probe the relationship between local structure and dynamics near the glass transition. We calculate the Voronoi volume for our particles and show that this quantity is not a universal probe of glassy structure for all colloidal suspensions. We correlate the Voronoi volume to displacement and find that these quantities are only weakly correlated. We observe qualitatively similar results in a simulation of a polymer melt. These results suggest that the Voronoi volume does not predict dynamical behavior in experimental colloidal suspensions; a purely structural approach based on local single particle volume likely cannot describe the colloidal glass transition.     

Stability of sputter-deposited gold nanoparticles in imidazolium ionic liquids

The stability of gold nanoparticles synthesised by sputter deposition has been studied in situ in 1-butyl-3-methylimidazolium ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate and dicyanamide anions with UV-VIS absorption spectroscopy and transmission electron microscopy. Besides the growth of the gold nanoparticles, two other processes were observed after sputtering, namely aggregation and sedimentation of these nanoparticles. To model the absorption spectra of the sputtered gold nanoparticles, generalized multiparticle Mie calculations were performed. These theoretical calculations confirm the increase in absorbance at longer wavelength for larger aggregates and are in agreement with the experimental observations. It was found that the kinetics of aggregation and sedimentation scale with the viscosity of the ionic liquid. Small amounts of water were found to have a large detrimental influence on the stability of the colloidal suspensions of the gold nanoparticles in ionic liquids. From the large discrepancy between the theoretical and the experimentally observed stability of the NPs, it was concluded that structural forces stabilize the gold nanoparticles. This was also borne out by AFM measurements.     

Oriented attachment mechanism in anisotropic nanocrystals: a "polymerization" approach.

The kinetic model of stepwise polymerization is revisited, with some adaptations for its application to the kinetics of oriented attachment of nanoparticles in colloidal suspensions, which results in the formation of anisotropic particles. A comparison with experimental data reported in the literature shows good agreement with the model and supports comparisons with other systems.     

Dielectric relaxation pattern of dilute colloidal suspensions

An immediate method of analysis of the relaxation characteristics of a colloidal suspension, like of any dielectric, is based on the so-called Cole-Cole representation (imaginary part versus real part) of its complex dielectric constant in a wide frequency range. In this work, we show theoretical plots calculated according to the models developed by DeLacey and White (J Chem Soc Faraday Trans 2 77:2007–2039), and by Rosen et al. (J Chem Phys 98: 4183–4194; this model uses the dynamic Stern layer theory). Both theoretical approaches to the dielectric relaxation pattern of a colloidal suspension are compared to each other, and to experimental data obtained on polystyrene suspensions. Although no significant differences are found between the theoretical predictions of the relaxation patterns (except for the values of the dielectric constant; the DSL model yields higher polarizabilities of the suspensions), none of the models can exactly reproduce the frequency dependence of the dielectric constant of a colloidal system. We propose a modification of DeLacey and White's model to include the possibility that the ionic drag coefficients depend on the ion position in the double layer. The final results show that the general trends of the frequency dependence of the quantities involved are not modified, irregardless of the changes in ionic drag coefficients.     

Small-angle scattering as a tool for the study of microemulsion structure

Microemulsions are equilibrium dispersions of oil and water stabilized by a surfactant-rich sheet at the internal oil-water interfaces. The domains of oil and water have characteristic dimensions of a few hundred Ångstroms, and so are appropriate for study with small-angle scattering. The scattering from droplets of oil in water or water in oil may be modelled well with modern representations of the structure of colloidal suspensions, but the structure of microemulsions containing comparable amounts of oil and water is likely bicontinuous and is well represented as a disordered lamellar structure. Recent theoretical and experimental results are reviewed and extended.