Accounting for effective interactions among charged microgels.

We introduce a theoretical approach to describe structural correlations among charged permeable spheres at finite particle concentrations. This theory explicitly accounts for correlations among microions and between microions and macroions and allows for the proposal of an effective interaction among macroions that successfully captures structural correlations observed in poly-N-isopropyl acrylamide microgel systems. In our description the bare charge is fixed and independent of the microgel size, the microgel concentration, and the ionic strength, which contrasts with results obtained using linear response approximations, where the bare charge needs to be adapted to properly account for microgel correlations obtained at different conditions.

Evidence of electrostatic-enhanced depletion attraction in the structural properties and phase behavior of binary charged colloidal suspensions.

In this paper we study the structure and phase behavior of binary mixtures of charged particles at low ionic strength. Due to the large size asymmetry between both species, light scattering measurements give us access only to the partial static structure factor that corresponds to the big particles. We observe that the addition of small charged colloids produces a decrease of the main peak of the measured static structure factor and a shift to larger scattering vector values. This finding is in agreement with theory based on integral equations with the Hypernetted-Chain Closure (HNC) relation. The effective interaction between two big particles due to the presence of small particles is obtained by a HNC inversion scheme and used in numerical simulations that adequately reproduce the experiments. We find that the presence of small particles induces an electrostatic depletion screening among the big colloids, creating around them an exclusion zone for the small charged colloids greater than that caused in the case of neutral small colloids, which in turn augments the depletion effect.

Investigation of moderately turbid suspensions by heterodyne near field scattering.

Light scattering has proven to be a very powerful technique to characterize soft matter systems. However, many samples are turbid and hence suffer from multiple scattering which can affect the signal considerably. Multiple scattering can be reduced by diluting the sample or changing the solvent, but often this alters the sample and hence is precluded. Here we study the dynamics of a model system. In particular, we investigate the effects of moderate multiple scattering on small-angle heterodyne near field scattering (HNFS). Varying the particle concentration and size we change the degree of multiple scattering, which is quantified by the transmission of light. In dependence of the degree of multiple scattering, we analyze the statistical properties of the HNFS signal, which is the difference between two intensity patterns separated by a delay time. The distribution of intensity differences follows a Gaussian distribution if single scattering dominates and a Laplace distribution in the presence of extreme multiple scattering. We also investigate the effects of multiple scattering on the measured intermediate scattering function and the hydrodynamic radius of the particles. Reliable data are obtained for sample transmissions down to about 0.7. This is confirmed by a comparison with results from a far field cross-correlation instrument that suppresses multiple scattering contributions. Therefore, HNFS represents a technically simple but powerful method to investigate samples that are moderately multiple scattering.

Impact of volume transition on the net charge of poly-N-isopropyl acrylamide microgels.

We explore the electrostatic properties of poly-N-isopropyl acrylamide microgels in dilute, quasi-de-ionized dispersions and show that the apparent net charge of these thermosensitive microgels is an increasing function of their size, the size being conveniently varied by temperature. Our experimental results obtained in a combination of light scattering, conductivity, and mobility experiments are consistent with those obtained in Poisson-Boltzmann cell model calculations, effectively indicating that upon shrinking the number of counterions entrapped within the microgels increases. Remarkably, this behavior shows that the electrostatic energy per particle remains constant upon swelling or deswelling the microgel, resulting in a square root dependence of the net charge on the particle radius.

On the calculation of the structure of charge-stabilized colloidal dispersions using density-dependent potentials.

The structure of charge-stabilized colloidal dispersions has been studied through a one-component model using a Yukawa potential with density-dependent parameters examined with integral equation theory and Monte Carlo simulations. Partial thermodynamic consistency was guaranteed by considering the osmotic pressure of the dispersion from the approximate mean-field renormalized jellium and Poisson-Boltzmann cell models. The colloidal structures could be accurately described by the Ornstein-Zernike equation with the Rogers-Young closure by using the osmotic pressure from the renormalized jellium model. Although we explicitly show that the correct effective pair-potential obtained from the inverse Monte Carlo method deviates from the Yukawa shape, the osmotic pressure constraint allows us to have a good description of the colloidal structure without losing information on the system thermodynamics. Our findings are corroborated by primitive model simulations of salt-free colloidal dispersions.

Three dimensional cross-correlation dynamic light scattering by non-ergodic turbid media.

We investigate dynamic light scattering by non-ergodic turbid media with an adapted version of the method proposed by Pusey and van Megen [Physica A 157, 705 (1989)]. Our formulation follows the derivation of the original method by extending it to the three dimensional cross-correlation scheme (3DDLS). The main finding is an expression to obtain the dynamic structure factor from light scattering that takes into account the system turbidity and the peculiarities of the 3D geometry. From 3DDLS measurements in well-controlled solid-like systems of different turbidity, we confirm that our results can be interpreted reasonably well by the theoretical approach described here. Good agreement is found with earlier reported results on similar systems.

Dynamic arrest in charged colloidal systems exhibiting large-scale structural heterogeneities.

Suspensions of charged liposomes are found to exhibit typical features of strongly repulsive fluid systems at short length scales, while exhibiting structural heterogeneities at larger length scales that are characteristic of attractive systems. We model the static structure factor of these systems using effective pair interaction potentials composed of a long-range attraction and a shorter range repulsion. Our modeling of the static structure yields conditions for dynamically arrested states at larger volume fractions, which we find to agree with the experimentally observed dynamics.

Density dependent interactions and structure of charged colloidal dispersions in the weak screening regime.

We determine the structure of charge-stabilized colloidal suspensions at low ionic strength over an extended range of particle volume fractions using a combination of light and small angle neutron scattering experiments. The variation of the structure factor with concentration is analyzed within a one-component model of a colloidal suspension. We show that the observed structural behavior corresponds to a nonmonotonic density dependence of the colloid effective charge and the mean interparticle interaction energy. Our findings are corroborated by similar observations from primitive model computer simulations of salt-free colloidal suspensions.

Macroion correlation effects in electrostatic screening and thermodynamics of highly charged colloids.

We study macroion correlation effects on the thermodynamics of highly charged colloidal suspensions using a mean-field theory and primitive model computer simulations. We suggest a simple way to include the macroion correlations into the mean-field theory as an extension of the renormalized jellium model of Trizac and Levin [Phys. Rev. E 69, 031403 (2004)]. The effective screening parameters extracted from our mean-field approach are then used in a one-component model with macroions interacting via a Yukawa-like potential to predict macroion distributions. We find that inclusion of macroion correlations leads to a weaker screening and hence smaller effective macroion charge and lower osmotic pressure of the colloidal dispersion as compared to other mean-field models. This result is supported by comparison to primitive model simulations and experiments for charged macroions in the low-salt regime, where the macroion correlations are expected to be significant.

Photonic properties of strongly correlated colloidal liquids.

The optical and structural properties of dense colloidal suspensions in the presence of long-range electrostatic repulsion are determined from both light and small-angle neutron scattering experiments. Short-range structural order induces an enhancement of the scattering strength while at the same time the total transmission shows strong wavelength dependence, reminiscent of a photonic crystal. Interestingly, the interplay between diffusive scattering and local order leads to negative values of the scattering anisotropy parameter. The tunable optical properties of these liquids furthermore suggest potential applications such as transparency switches or filters.

Diffusing wave spectroscopy and small-angle neutron scattering from concentrated colloidal suspensions.

We have studied the properties of dense colloidal suspensions with a combination of small-angle neutron scattering (SANS) and diffusing wave spectroscopy (DWS). Contrary to single light scattering, DWS provides dynamic information on length scales, from 1 to 100 nm, comparable to SANS. This offers a unique range of accessible length and time scales perfectly suited for the (noninvasive) investigation of highly concentrated systems. By this we obtain valuable information about the structural properties and the short-time diffusion of electrostatically stabilized, but strongly screened, hard-sphere-like colloidal suspensions with volume fractions up to 30%. We furthermore discuss the consequences of local structural ordering on the optical properties, such as optical density and polarization. Quantitative agreement is found when comparing transmission measurements (optical density) with parameter-free numerical calculations based on the structural characterization from SANS.

Structure, dynamics, and optical properties of concentrated milk suspensions: an analogy to hard-sphere liquids.

A systematic study of the effects of volume fraction increment on the optical properties, the structure, and the dynamics of the casein micelles and fat droplets in milk was performed using diffusing wave spectroscopy. Four types of milk were investigated, NIDO full fat milk, fat-free milk, whey and fat-free milk, and finally lactose and fat-free milk. Independent measurements to calculate the dependence of the viscosity and the index of refraction of the milk serum and casein micelles as a function of the volume fraction were also performed. We compare the experimentally determined quantities photon transport mean free path (l*) and self-diffusion coefficient D(s) with the predictions from theoretical calculations using classical colloidal models such as a hard-sphere fluid. We demonstrate that all types of milk with and without fat content behave, structurally, like colloidal hard-sphere systems up to volume fractions well over 45%. In the case of dynamic measurements, both lactose- and fat-free and whey- and fat-free milk behave also like hard-sphere systems whereas fat-free milk and fat-containing NIDO milk deviate slightly at volume fractions over 35%. Finally, a comparative measurement and theoretical calculation of the casein micelle's size was performed.