Hydrodynamic and Colloidal Interactions in Concentrated Charge-Stabilized Polymer Dispersions

Hydrodynamic and colloidal interactions are explored in concentrated, charge-stabilized colloidal dispersions by measuring the dependence of rheology (e.g., low and high-shear viscosity, high-frequency viscosity, and modulus) and self-diffusivity on salt content, particle size, and concentration. Model, sulfonated polystyrene lactices of varying diameter are prepared and investigated by shear rheology, high-frequency torsional resonance, electrophoresis, titration, and dynamic light scattering. The high-frequency and high-shear viscosity both are dominated by hydrodynamic interactions, but are shown not to be identical, due to the microstructure distortion resulting from high shear rates. The short-time self-diffusion is also shown to be insensitive to direct particle interactions, but has a different concentration dependence than the high-frequency viscosity, further illustrating a predicted violation of a generalized Stokes-Einstein relationship for these properties. The apparent colloidal surface charge is extracted from the high-frequency elastic modulus measurements on concentrated dispersions. The surface charge is in good agreement with results from critical coagulation concentration measurements and perturbation theories, but disagrees with electrophoretic mobility experiments. This indicates that the effective surface charge determined by torsional high-frequency measurements is a more reliable predicter of the salt stability of charge-stabilized dispersions, in comparison to zeta-potentials determined from electrophoretic mobilities. Further, we demonstrate by direct comparison that measurements of the apparent plateau modulus by rotational rheometry underestimate the true, high-frequency modulus and provide unreliable estimates for the surface charge. Copyright 2000 Academic Press.     

The polydisperse cell model: nonlinear screening and charge renormalization in colloidal mixtures

We propose a model for the calculation of renormalized charges and osmotic properties of mixtures of highly charged colloidal particles. The model is a generalization of the cell model and the notion of charge renormalization as introduced by Alexander et al. [J. Chem. Phys. 80, 5776 (1984)]. The total solution is partitioned into as many different cells as components in the mixture. The radii of these cells are determined self-consistently for a given set of parameters from the solution of the nonlinear Poisson-Boltzmann equation with appropriate boundary conditions. This generalizes Alexanders's model where the (unique) Wigner-Seitz cell radius is solely fixed by the colloid packing fraction. We illustrate the technique by considering a binary mixture of the colloids with the same sign of charge. The present model can be used to calculate thermodynamic properties of highly charged colloidal mixtures at the level of linear theories, while taking the effect of nonlinear screening into account.     

Entropic effects in the electric double layer of model colloids with size-asymmetric monovalent ions

The structure of the electric double layer of charged nanoparticles and colloids in monovalent salts is crucial to determine their thermodynamics, solubility, and polyion adsorption. In this work, we explore the double layer structure and the possibility of charge reversal in relation to the size of both counterions and coions. We examine systems with various size-ratios between counterions and coions (ion size asymmetries) as well as different total ion volume fractions. Using Monte Carlo simulations and integral equations of a primitive-model electric double layer, we determine the highest charge neutralization and electrostatic screening near the electrified surface. Specifically, for two binary monovalent electrolytes with the same counterion properties but differing only in the coion's size surrounding a charged nanoparticle, the one with largest coion size is found to have the largest charge neutralization and screening. That is, in size-asymmetric double layers with a given counterion's size the excluded volume of the coions dictates the adsorption of the ionic charge close to the colloidal surface for monovalent salts. Furthermore, we demonstrate that charge reversal can occur at low surface charge densities, given a large enough total ion concentration, for systems of monovalent salts in a wide range of ion size asymmetries. In addition, we find a non-monotonic behavior for the corresponding maximum charge reversal, as a function of the colloidal bare charge. We also find that the reversal effect disappears for binary salts with large-size counterions and small-size coions at high surface charge densities. Lastly, we observe a good agreement between results from both Monte Carlo simulations and the integral equation theory across different colloidal charge densities and 1:1-electrolytes with different ion sizes.     

Phase Transitions of the Liquid–Liquid Type and a Change in the Particle Charge in Colloidal Solutions

The thermodynamic properties are studied for the solutions of charged colloidal particles with ionizable surface groups. The microscopic mechanism of microion binding at surface groups is considered. The free energy of the system in the parameter range where the usual theory of such solutions is inadequate (a range of practical interest) is calculated using the method of the thermodynamic perturbation theory. The first-order phase transition of the liquid–liquid type is shown to be possible; in this phase transition, a phase with a high concentration of colloidal particles that have a higher charge coexists with a phase with a lower concentration of particles that have a lower charge.     

Effects of structural properties of the Stern layer on the electrophoretic migration of a highly charged spherical macroion

The electrophoretic migration of a highly charged spherical macroion suspended in an aqueous solution of NaCl is studied using the molecular dynamic method. The objective is to examine the effects of the colloidal surface charge density on the electrophoretic mobility (μ) of the spherical macroion. The bare charge and the size of the macroion are varied separately to induce changes in the colloidal surface charge density. Our results indicate that μ depends on colloidal surface charge density in a nonmonotonic manner, but that this relationship is independent of the way the surface charge density is varied. It is found that an increase in colloidal surface charge density may lead to the formation of new sublayers in the Stern layer. The μ profile is also found to have a local maximum for a bare charge at which a new sublayer is formed in the Stern layer, and a local minimum for a bare charge at which the outer sublayer becomes relatively dense. Finally, the electrophoretic flow caused by the migration of the spherical macroion is studied to find that one decisive factor causing the electrophoretic flow is the ability of the macroion to carry anions in the electrolyte solution.     

Electrokinetic behavior and colloidal stability of polystyrene latex coated with ionic surfactants

This work is focused on analyzing the electrokinetic behavior and colloidal stability of latex dispersions having different amounts of adsorbed ionic surfactants. The effects of the surface charge sign and value, and the type of ionic surfactant were examined. The analysis of the electrophoretic mobility (mu(e)) versus the electrolyte concentration up to really high amounts of salt, much higher than in usual studies, supports the colloidal stability results. In addition, useful information to understand the adsorption isotherms was obtained by studying mu(e) versus the amount of the adsorbed surfactant. Aggregation studies were carried out using a low-angle light scattering technique. The critical coagulation concentrations (ccc) of the particles were obtained for different surfactant coverage. For latex particles covered by ionic surfactants, the electrostatic repulsion was, in general, the main contribution to the colloidal stability of the system; however, steric effects played an important role in some cases. For latices with not very high colloidal stability, the adsorption of ionic surfactants always improved the colloidal stability of the dispersion above certain coverage, independently of the sign of both, latex and surfactant charge. This was in agreement with higher mobility values. Several theoretical models have been applied to the electrophoretic mobility data in order to obtain different interfacial properties of the complexes (i.e., zeta potential and density charge of the surface charged layer).     

Cationic gel-phase liposomes with "decorated" anionic SPIO nanoparticles: morphology, colloidal, and bilayer properties

The assembly and complexation of oppositely charged colloids are important phenomena in many natural and synthetic processes. Liposome-nanoparticle assemblies (LNAs) represent an interesting hybrid system that combines "soft" and "hard" colloidal materials. This work describes the formation and characterization of gel-phase LNAs formed by the binding of anionic superparamagnetic iron oxide (SPIO) nanoparticles to cationic dipalmitoylphosphatidylcholine (DPPC)/dipalmitoyltrimethylammonium propane (DPTAP) liposomes. Particles were examined with hydrodynamic diameters below (16 nm) and above (30 nm) the cutoff reported for supported lipid bilayer formation. LNA formation with 16 nm particles was entropically driven and particles bound individually to yield "decorated" structures. In this case, increasing nanoparticle concentration yielded colloidal LNA aggregates and eventual charge inversion. In contrast, LNA formation with 30 nm particles was enthalpically driven, and the nanoparticles aggregated at the bilayer interface. These aggregates led to significant LNA aggregation and large bilayer sheets due to liposome rupture despite minimal charge screening of the liposome surface. In this case SLBs were present, but these structures were not dominant. Differences in LNA structure were also revealed through the lipid phase transition behavior. This work infers size-dependent nanoparticle binding and LNA formation mechanisms that can be used to tailor colloidal and bilayer properties. Analogies are made to polyelectrolyte patch charge heterogeneities and DNA complexation with cationic liposomes.     

银溶胶的形成及在光度分析中的作用

氢化物与硝酸银反应形成银溶胶的分光光度法,具有操作简便、分析速度快、灵敏度高和应用范围广等特点,深入探讨银溶胶的物理和化学性质对改进此方法的实验条件,增强银溶胶的稳定性和改善方法的重现性,以及提高方法的灵敏度和选择性等都有重要的意义,我们以铅烷与硝酸银的反应产物为研究对象,用X光小角散射仪、透射电子显微镜和光     

Effect of a surface charge on the halfwidth and peak position of cluster plasmons in colloidal metal particles

The optical response of colloidal particles depends on a variety of properties of the cluster, e.g., shape, size, size distribution and particle material. Since particles often are charged, also the surface charge may be a parameter which influences their optical properties. In this paper the effect of a surface charge on optical properties of spherical colloidal particles is studied and its magnitude is estimated by extended computations for silver clusters with surface plasmon in aqueous suspension. Two models are presented and discussed. The first model is based on the electrodynamic solution by Bohren and Hunt (Can. J. Phys. 55, 1930 (1977)), where a surface conductivity _S for a free surface charge yield an additional contribution _S to the dielectric constant of the particle material. In the second model, the surface charge contributes to the number density of free electrons in the cluster. Both models lead to a shift of the cluster plasmon peak, while an increase of the plasmon halfwidth could not be derived. The effect is quite small and limited on very small clusters.PACS 61.46+w 73.20.Mf 78.20.Dj     

Direct surface force measurement in water using a nanosize colloidal probe technique

The direct force measurement between colloidal surfaces has been an essential topic in both theories and applications of surface chemistry. As particle size is decreased from micron size down to true nano size (<10 nm), surface forces are increasingly important. Nanoparticles at close proximity or high solids loading are expected to show a different behavior than what can be estimated from continuum and mean field theories. The current tools for directly measuring interaction forces such as a surface force apparatus or atomic force microscopy (AFM) are limited to particles much larger than nanosize. Here a modified colloidal probe technique is suggested using a multiwalled carbon nanotube (MWNT) to overcome this problem. Determination of zero separation in AFM is critical to extract a reliable force-separation curve when MWNT is used as a probe. Hence, a systematic approach to the data collection for a nanosize colloidal probe is proposed and a sample of a direct surface force measurement curve obtained with the MWNT probe is presented.     

Ionic correlations in highly charge-asymmetric colloidal liquids

We use electrophoretic mobility (mu) measurements of charged colloidal particles under the presence of multivalent counterions as a probe of the electrostatic correlations between them; they become important for sufficiently high surface charge densities of the colloid (sigma) and result in a decreasing mu upon increasing sigma. The physics of this decrease is the same as that giving rise to charge inversion. We account qualitatively for the observations by considering recent theoretical arguments that assume the counterions next to the colloid surface as a strongly correlated liquid of properties similar to that of a Wigner crystal.     

Hydrolysis versus ion correlation models in electrokinetic charge inversion: establishing application ranges

In this article, we investigate experimentally a wide range of situations where charge inversion (i.e., overcompensation of the surface charge of a colloidal particle by the countercharge) can occur. To that end, the electrophoretic mobility of sodium montmorillonite, silica, and polystyrene latex as functions of pH and concentration of different salts is presented, and conditions are established where charge inversion occurs. The reason for this study is to provide experimental evidence for distinguishing between two existing models for the explanation of charge inversion. One of these is the specific adsorption of ions located in the Stern layer in combination with a Gouy-Chapman diffuse part of the double layer. The other ion-correlation theories explain the phenomenon in terms of purely physical arguments based on Coulombic pair interactions between ions and surface charges and on excluded volume effects. In distinguishing between these two interpretations, the influence of the pH plays a central role because of its effect on the hydrolysis of multivalent cations. In our experiments, it is found that although 1-2 and 2-2 electrolytes provoke a decrease in the absolute values of the electrophoretic mobilities when their concentration in solution is increased, they never lead to charge inversion, whatever the surface charge or the pH. However, in the case of salts of trivalent cations, electrokinetic charge reversal is often observed above a certain critical electrolyte concentration. In addition, the extent of overcharging increases when the concentration is raised above the critical value. This trend occurs for any system in which the surface charge is pH-independent, as in polystyrene latex and montmorillonite. Most of the results presented here are compatible with the specific adsorption of hydrolyzed metal ions as the main driving force for charge inversion. At low pH, when the hydrolysis of trivalent cations is likely to be absent, overcharging can be attributed to ion correlation effects.     

Thermodiffusion of charged colloids: single-particle diffusion

An expression for the single-particle thermal diffusion coefficient of a charged colloidal sphere is derived on the basis of force balance on the Brownian time scale in combination with thermodynamics. It is shown that the single-particle thermal diffusion coefficient is related to the temperature dependence of the reversible work necessary to build the colloidal particle, including the core, the solvation layer, and the electrical double layer. From this general expression, an explicit expression for the contribution of the electrical double layer to the single-particle thermal diffusion coefficient is derived in terms of the surface charge density of the colloidal sphere, the electrostatic screening length, and its core radius, to within the Debye-Hückel approximation. This result is shown to explain experimental data, for both thin and thick double layers. In addition, a comparison with other theories is made.     

Comparison of USAXS information with RMSA prediction for the effect of added salt on colloidal crystal structure

Charged colloidal particles form so‐called colloidal crystals in dispersions because of electrostatic interparticle interactions between them. We performed a systematic and quantitative investigation of the effect of salt on the interparticle distance in colloidal crystals with the ultra‐small‐angle X‐ray scattering (USAXS) technique. We accumulated a great deal of significant information about the mechanism of the colloidal crystal formation by USAXS. We found that the interparticle distance in colloidal crystals shows a maximum as a function of the added salt concentration. The maximum position of the interparticle distance was located around κa = 1.3 (κ⁻¹ is the Debye length, and a is the particle radius). The behavior of the decrease of the interparticle distance with the increase of the added salt concentration at κa > 1.3 could be explained not quantitatively but qualitatively with the effective hard‐sphere theory. Thus, it was suggested that the dependence of the interparticle distance on the salt concentration at κa > 1.3 was reasonable according to the classical theories, such as the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. In this article, we advance this theoretical approach with the classical theory, that is, with the assumption of the only repulsive force for the interparticle interaction, to elucidate the origin of the curious behavior of the interparticle distance. We estimated the structure factor by the rescaled mean spherical approximation (RMSA) with a Yukawa‐type interparticle interaction potential. A comparison between the prediction of the RMSA data and USAXS experimental data was performed. In this analysis, the charge renormalization procedure was applied. Although the origin of the behavior of the interparticle distance at κa < 1.3 is still a mystery, we concluded that the behavior at κa > 1.3 could be interpreted as a result from the DLVO manner. The effective surface charge number was on the order of several percentages of the analytical surface charge number. This experimental fact certainly proves the validly of our USAXS observation quantitatively and also predicts the existence of novel factors for κa ≤ 1.3, the real origin of colloidal crystal formation, which have never been taken into account previously. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 78–90, 2001     

Ultrasmall iron oxide nanoparticles for biomedical applications: improving the colloidal and magnetic properties

A considerable increase in the saturation magnetization, M(s) (40%), and initial susceptibility of ultrasmall (<5 nm) iron oxide nanoparticles prepared by laser pyrolysis was obtained through an optimized acid treatment. Moreover, a significant enhancement in the colloidal properties, such as smaller aggregate sizes in aqueous media and increased surface charge densities, was found after this chemical protocol. The results are consistent with a reduction in nanoparticle surface disorder induced by a dissolution-recrystallization mechanism.     

Probing surface charge potentials of clay basal planes and edges by direct force measurements

The dispersion and gelation of clay suspensions have major impact on a number of industries, such as ceramic and composite materials processing, paper making, cement production, and consumer product formulation. To fundamentally understand controlling mechanisms of clay dispersion and gelation, it is necessary to study anisotropic surface charge properties and colloidal interactions of clay particles. In this study, a colloidal probe technique was employed to study the interaction forces between a silica probe and clay basal plane/edge surfaces. A muscovite mica was used as a representative of 2:1 phyllosilicate clay minerals. The muscovite basal plane was prepared by cleavage, while the edge surface was obtained by a microtome cutting technique. Direct force measurements demonstrated the anisotropic surface charge properties of the basal plane and edge surface. For the basal plane, the long-range forces were monotonically repulsive within pH 6-10 and the measured forces were pH-independent, thereby confirming that clay basal planes have permanent surface charge from isomorphic substitution of lattice elements. The measured interaction forces were fitted well with the classical DLVO theory. The surface potentials of muscovite basal plane derived from the measured force profiles were in good agreement with those reported in the literature. In the case of edge surfaces, the measured forces were monotonically repulsive at pH 10, decreasing with pH, and changed to be attractive at pH 5.6, strongly suggesting that the charge on the clay edge surfaces is pH-dependent. The measured force profiles could not be reasonably fitted with the classical DLVO theory, even with very small surface potential values, unless the surface roughness was considered. The surface element integration (SEI) method was used to calculate the DLVO forces to account for the surface roughness. The surface potentials of the muscovite edges were derived by fitting the measured force profiles with the surface element integrated DLVO model. The point of zero charge of the muscovite edge surface was estimated to be pH 7-8.     

Polymeric membranes: Surface modification for minimizing (bio)colloidal fouling

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London–van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized.     

Self-assembly of fatty acids in the presence of amines and cationic components

Fatty acids can self-assemble under various shapes in the presence of amines or cationic components. We assemble and compare these types of self-assembly leading toward a catanionic system either with a cationic surfactant or with an amine component playing the role of counter-ion. First, we focus on the molar ratio as a key driving parameter. Known and yet un-known values from other quantities governing the colloidal properties of these systems such as structural surface charge, osmotic pressure, molecular segregation, rigidity, in plane colloidal interactions and melting transition are discussed. We include also recent results obtained on the interfacial and foaming properties of these systems. We will highlight the specificity of these self-assemblies leading to unusual macroscopic properties rich of robust applications.     

On the Applicability of DLVO Theory to the Prediction of Clay Colloids Stability

The stability behavior of Na-montmorillonite colloids has been studied by combining the analysis of their surface charge properties and time-resolved dynamic light scattering experiments. The chemical surface model for several types of clays, including montmorillonite, has to take into account the double surface charge contribution due to their permanent structural charge and to their pH-dependent charge, which is developed at the edge sites, therefore, these stability studies were carried out as a function of both ionic strength and pH. DLVO theory is largely applied for the prediction of the stability of many colloidal systems, including the natural ones. This work shows that the stability behavior of Na-montmorillonite colloids cannot be satisfactorily reproduced by DLVO theory, using the surface parameters experimentally obtained. Particularly, this theory is unable to explain their pH-dependent stability behavior caused by the small charge at the edge sites. Based on these results, a literature review of DLVO stability prediction of clay colloids was performed. It confirmed that this theory is not capable of taking into account the double contribution to the total surface charge and, at the same time, pointed out the main uncertainties related to the appropriate use of the input parameters for the calculation as, for example, the Hamaker constant or the surface potential. Copyright 2000 Academic Press.     

Effect of additives on electrokinetic properties of colloidal alumina suspension

Additive interactions and their effects on electrokinetic properties of colloidal alumina suspension are presented in this study. Dibasic ammonium citrate (DAC), natural egg albumin, and octanol-2 are chosen as additives. The surface charge behavior of a 5% (w/v) colloidal alumina suspension in the presence of these additives has been studied in detail. The optimum dosage of DAC to have a stable suspension is found to be 3 mg/g of alumina whereas it is 105 and 164 mg/g of alumina for albumin and octanol-2, respectively. Albumin was found to be a better dispersant than DAC and interacts more strongly than DAC with the surface of alumina, while octanol-2 shows physisorbing characteristics. Turbidity measurements indicate that albumin and DAC interact. When the DAC : albumin molar ratio exceeds 10, the turbidity of the solution is higher than the turbidity of pure albumin, indicating the formation of complexes.