Interaction forces between colloidal particles in a solution of like-charged, adsorbing nanoparticles

We have measured the force between a weakly charged micron-sized colloidal particle and flat substrate in the presence of highly charged nanoparticles of the same sign under solution conditions such that the nanoparticles physically adsorb to the colloidal particle and substrate. The objective was to investigate the net effect on the force profile between the microparticle and flat substrate arising from both nanoparticle adsorption and nanoparticles in solution. The experiments used colloidal probe atomic force microscopy (CP-AFM) to measure the force profile between a relatively large (5 μm) colloidal probe glass particle and a planar glass substrate in aqueous solutions at varying concentrations of spherical nanoparticles. At very low nanoparticle concentrations, the primary effect was an increase in the electrostatic repulsion between the surfaces due to adsorption of the more highly charged nanoparticles. As the nanoparticle concentration is increased, a depletion attraction formed, followed by longer-range structural forces at the highest nanoparticle concentrations studied. These results suggest that, depending on their concentration, such nanoparticles can either stabilize a dispersion of weakly-charged colloidal particles or induce flocculation. This behavior is qualitatively different from that in nonadsorbing systems, where the initial effect is the development of an attractive depletion force.     

Electrostatic interactions between amphoteric latex particles and proteins

The electrostatic interactions between amphoteric polymethyl methacrylate latex particles and proteins with different pI values were investigated. These latex particles possess a net positive charge at low pH, but they become negatively charged at high pH. The nature and degree of interactions between these polymer particles and proteins are primarily controlled by the electrostatic characteristics of the particles and proteins under the experimental conditions. The self-promoting adsorption process from the charge neutralization of latex particles by the proteins, which have the opposite net charge to that of the particles, leads to a rapid reduction in the zeta potential of the particles (in other words colloidal stability), and so strong flocculation occurs. On the other hand, the electrostatic repulsion forces between similarly charged latex particles and the proteins retard the adsorption of protein molecules onto the surfaces of the particles. Therefore, latex particles exhibit excellent colloidal stability over a wide range of protein concentrations. A transition from net negative charge to net positive charge, and vice versa (charge reversal), was observed when the particle surface charge density was not high enough to be predominant in the protein adsorption process.     

Improved dewatering behavior of clay minerals dispersions via interfacial chemistry and particle interactions optimization

Orthokinetic flocculation of clay dispersions at pH 7.5 and 22 degrees C has been investigated to determine the influence of interfacial chemistry and shear on dewatering and particle interactions behavior. Modification of pulp chemistry and behavior was achieved by using kaolinite and Na-exchanged (swelling) smectite clay minerals, divalent metal ions (Ca(II), Mn(II)) as coagulants and anionic polyacrylamide copolymer (PAM A) and non-ionic polyacrylamide homopolymer (PAM N) as flocculants. The pivotal role of shear, provided by a two-blade paddle impeller, was probed as a function of agitation rate (100-500 rpm) and time (15/60 s). Particle zeta potential and adsorption isotherms were measured to quantify the interfacial chemistry, whilst rheology and cryogenic SEM were used to investigate particle interactions and floc structure and aggregate network, respectively. Osmotic swelling, accompanied by the formation of "honeycomb" particle network structure and high yield stress, was produced by the Na-exchanged smectite, but not kaolinite, dispersions. Dispersion of the clay particles in 0.05 M Ca(II) or Mn(II) solution led to a marked reduction in particle zeta potential, complete suppression of swelling, honeycomb network structure collapse and a concomitant reduction in shear yield stress of smectite pulps. Optimum conditions for improved, orthokinetic flocculation performance of negatively charged clay particles, reflecting faster settling flocs comprised (i) coagulation, (ii) moderate agitation rate, (iii) shorter agitation time, and (iv) anionic rather than non-ionic PAM. The optimum dewatering rates were significantly higher than those produced by standard, manual-mixing flocculation techniques (plunging and cylinder inversion) commonly used in industry for flocculant trials. The optimum flocculation conditions did not, however, have a significant impact on the final sediment solid content of 20-22 wt%. Further application of shear to pre-sedimented pulps improved consolidation by 5-7 wt% solid. Higher shear yield stresses and greater settling rates were displayed by PAM A based than PAM N based pulps and this is attributed to the former's more expanded interfacial conformation and greater clay particles bridging ability. It appears that the intrinsic clay particles' physico-chemical properties and interactions limit compact pulp consolidation.     

Effect of dispersion pH on the formation and stability of Pickering emulsions stabilized by layered double hydroxides particles

Using positively charged plate-like layered double hydroxides (LDHs) particles as emulsifier, liquid paraffin-in-water emulsions stabilized solely by such particles are successfully prepared. The effects of the pH of LDHs aqueous dispersions on the formation and stability of the emulsions are investigated here. The properties of the LDHs dispersions at different pHs are described, including particle zeta potential, particle aggregation, particle contact angle, flow behavior of the dispersions and particle adsorption at a planar oil/water interface. The zeta potential decreases with increasing pH, leading to the aggregation of LDHs particles into large flocs. The structural strength of LDHs dispersions is enhanced by increasing pH and particle concentration. The three-phase contact angle of LDHs also increases with increasing pH, but the variation is very small. Visual observation and SEM images of the interfacial particle layers show that the adsorption behavior of LDHs particles at the planar oil/water interface is controlled by dispersion pH. We consider that the particle-particle (at the interface) and particle-interface electrostatic interactions are well controlled by adjusting the dispersion pH, leading to pH-tailored colloid adsorption. The formation of an adsorbed particle layer around the oil drops is crucial for the formation and stability of the emulsions. Emulsion stability improves with increasing pH and particle concentration because more particles are available to be adsorbed at the oil/water interface. The structural strength of LDHs dispersions and the gel-like structure of emulsions also influence the stability of the emulsions, but they are not necessary for the formation of emulsions. The emulsions cannot be demulsified by adjusting emulsion pH due to the irreversible adsorption of LDHs particles at the oil/water interface. TEM images of the emulsion drops show that a thick particle layer forms around the oil drops, confirming that Pickering emulsions are stabilized by the adsorbed particle layers. The thick adsorbed particle layer may be composed of a stable inner particle layer which is in direct contact with the oil phase and a relatively unstable outer particle layer surrounding the inner layer.     

Measurement of Colloidal Stability in Solutions of Simple, Nonadsorbing Polyelectrolytes

The stability of a solution of charged polystyrene particles in the presence of nonadsorbing polyelectrolyte macromolecules is measured using optical light scattering. The particles were negatively charged polystyrene latex spheres (0.5–1 μm diameter) while the macromolecules were simulated using negatively charged colloidal silica spheres (5–7 nm diameter). Because of the electrostatic repulsion between the particles, the solution is found to be stable against primary flocculation (irreversible flocculation into a primary energy minima). However, because of long-range attractive depletion forces, reversible secondary flocculation of the particles occurs into a local potential energy minimum. As observed with uncharged macromolecules, the polyelectrolyte first induces flocculation at a critical flocculation concentration (v*), but later restabilizes the system at a critical restabilization concentration (v**). These critical concentrations are found to decrease with decreasing macromolecule size and increasing particle size. The restabilized solutions are found to remain suspended for periods greater than 20 days. Comparison of the measured flocculation and restabilization results to predictions made using a recently developed force-balance model show qualitative agreement.     

Computer Simulation of Bridging Flocculation Processes: The Role of Colloid to Polymer Concentration Ratio on Aggregation Kinetics

The flocculation of colloidal particles by adsorbing polymers is one of the central issues of colloid science and a very important topic in many industrial, biological, and environmental processes. We report a computer simulation study of a 2- and 3-dimensional model for bridging flocculation betweenlarge linear polymer chains and comparatively small colloidal particles,where the structure and growth kinetics of cluster formation are investigated. This model was developed within the framework of the cluster–cluster aggregation model using mass and fractal dimension dependent diffusion constants, where bridging flocculation is seen as a case of heterocoagulation in which, in addition, macromolecule configurations and lengths play an important role. The simulation of aggregate structure and formation kinetics obtained at different (i) relative particle concentrations, (ii) polymer chain conformations, and (iii) sticking probabilities are described from a qualitatively and quantitative point of view. The results suggest that the formation of large aggregates is a slow process, controlled by the reactivity of the clusters, even when the reaction between microcolloids and macrochains is very fast. Aggregation kinetics are strongly dependent on the particle/chain concentration ratio and on the configurational properties of the chains. It is shown that the scaling laws which are valid for homocoagulation processes are also applicable to the kinetics of bridging flocculation. The corresponding scaling exponents have been calculated.     

One-directional crystal growth in charged colloidal silica dispersions driven by diffusion of base

Aqueous dispersions of charged colloidal silica particles showed a novel one-directional crystal growth by diffusion of a weak base, pyridine. The colloidal crystal consisted of pillar-shaped crystal grains whose height and width were in the order of centimeter and subcentimeter, respectively. The growth process was explainable in terms of (i) the diffusion of pyridine with neutralization reactions between weakly acidic silica surfaces, (ii) charging up of the silica particles, and (iii) the charge-induced crystallization of the dispersions.     

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).     

Growth of colloidal aggregates through polymer bridging

The stability of colloidal dispersions can be altered through the addition of adsorbing macromolecules. Adsorption of macromolecules on the particle surfaces results in a stepwise aggregation process. We consider the early destabilization steps for nanometric ceria particles dispersed in water. These steps have been characterized through light scattering; they are: i) finite multiplets involving one macromolecule and a small number of particles; ii) bridging between mul tiplets; iii) formation of three-dimensional network of bridges. Each stage can be obtained as an equilibrium state, provided there is an adequate balance of electrostatic repulsions and polymer-induced attractions. Altering this balance may push the system from one state into another, or it may change the structure within one state. For instance, multiplets may be pushed to bind more particles or spill them out, depending on the equilibrium length of bridge; gels may reject solvent and turn into flocs if the equilibrium length of bridges becomes shorter than the average distance between particles.     

Effect of temperature on the reentrant condensation in polyelectrolyte-liposome complexation

Interactions of oppositely charged macroions in aqueous solution give rise to intriguing aggregation phenomena, resulting in finite-size, long-lived clusters, characterized by a quite narrow size distribution. Particularly, the adsorption of highly charged linear polyelectrolytes on oppositely charged colloidal particles is strongly correlated and some short-range order arises from competing electrostatic interactions between like-charged polymer chains (repulsion) and between polymer chains and particle surface (attraction). In these systems, in an interval of concentrations around the isoelectric point, relatively large clusters of polyelectrolyte-decorated particles form. However, the mechanisms that drive the aggregation and stabilize, at the different polymer/particle ratios, a well-defined size of the aggregates are not completely understood. Nor is clear the role that the correlated polyion adsorption plays in the aggregation, although the importance of "patchy interactions" has been stressed as the possible source of attractive interaction term between colloidal particles. Different models have been proposed to explain the formation of the observed cluster phase. However, a central question still remains unanswered, i.e., whether the clusters are true equilibrium or metastable aggregates. To elucidate this point, in this work, we have investigated the effect of the temperature on the cluster formation. We employed liposomes built up by DOTAP lipids interacting with a simple anionic polyion, polyacrylate sodium salt, over an extended concentration range below and above the isoelectric condition. Our results show that the aggregation process can be described by a thermally activated mechanism.     

The effect of block copolymer EPE1100 on the colloidal stability of Mg-Al LDH dispersions

The adsorption isotherm of block copolymer EPE1100 (polyethylene oxide-polypropylene oxide-polyethylene oxide) on the surfaces of Mg-Al LDH particles was determined through a solution depletion method combined with TOC measurement. X-ray diffraction patterns showed that the adsorption of EPE1100 molecules only occurred on the outer surfaces of LDH particles and they did not intercalate into the galleries between the layers. The adsorption of EPE1100 molecules changed the morphology of the particles. The effect of EPE1100 on the colloidal stability of LDH dispersion was investigated from three aspects: after the freezing-melting cycle, after the shearing rotations, and after the addition of electrolyte. The results indicated that the effect of EPE1100 on the colloidal stability of LDH dispersions was strongly related to the state of copolymer adsorption on LDH particle surfaces. It was inferred that the hydrated repulsive force and steric-repulsive force played important roles in determining the stability of the dispersions.     

Pickering emulsions stabilized solely by layered double hydroxides particles: the effect of salt on emulsion formation and stability

The formation and stability of liquid paraffin-in-water emulsions stabilized solely by positively charged plate-like layered double hydroxides (LDHs) particles were described here. The effects of adding salt into LDHs dispersions on particle zeta potential, particle contact angle, particle adsorption at the oil-water interface and the structure strength of dispersions were studied. It was found that the zeta potential of particles gradually decreased with the increase of salt concentration, but the variation of contact angle with salt concentration was very small. The adsorption of particles at the oil-water interface occurred due to the reduction of particle zeta potential. The structural strength of LDHs dispersions was strengthened with the increase of salt and particle concentrations. The effects of particle concentration, salt concentration and oil phase volume fraction on the formation, stability and type of emulsions were investigated and discussed in relation to the adsorption of particles at the oil-water interface and the structural strength of LDHs dispersions. Finally, the possible stabilization mechanisms of emulsions were put forward: the decrease of particle zeta potential leads to particle adsorption at the oil-water interface and the formation of a network of particles at the interface, both of which are crucial for emulsion formation and stability; the structural strength of LDHs dispersions is responsible for emulsion stability, but is not necessary for emulsion formation.     

Depletion flocculation of latex dispersion in ionic micellar systems

The flocculation behavior of anionic and cationic latex dispersions induced by addition of ionic surfactants with different polarities (SDS and cetyltrimethylammonium bromide (CTAB)) have been evaluated by rheological measurements. It was found that in identical polar surfactant systems with particle surfaces of SDS + anionic lattices and CTAB + cationic lattices, a weak and reversible flocculation has been observed in a limited concentration region of surfactant, which was analyzed as a repletion flocculation induced by the volume-restriction effect of the surfactant micelles. On the other hand, in oppositely charged surfactant systems (SDS + cationic lattices and CTAB + anionic lattices), the particles were flocculated strongly in a low surfactant concentration region, which will be based on the charge neutralization and hydrophobic effects from the adsorbed surfactant molecules. After the particles stabilized by the electrostatic repulsion of adsorbed surfactant layers, the system viscosity shows a weak maximum again in a limited concentration region. This weak maximum was influenced by the shear rate and has a complete reversible character, which means that this weak flocculation will be due to the depletion effect from the free micelles after saturated adsorption.     

Long‐term stability of an ambient self‐curable latex based on colloidal dispersions in water of two reactive polymers

An ambient self‐curable latex (ASCL) was prepared via the blending of colloidal dispersions in water of a chloromethylstyrene‐functionalized copolymer and a tertiary‐amine‐functionalized copolymer. Upon casting and drying under ambient conditions, the ASCL could generate crosslinked continuous polymer films. The crosslinking occurred via the Menschutkin reaction (quaternization) between the two types of functional groups. Because this reaction was reversible at high temperatures, the films could be decrosslinked and hence were self‐curable. The prepared ASCL exhibited excellent colloidal and chemical stability during long‐term storage: no significant changes in the colloidal properties, such as the particle size, electrophoretic mobility, and crosslinking reactivity, were observed after 48 months of storage. The electrophoretic measurements indicated that the electrostatic repulsion between the negatively charged particles of the ASCL was responsible for the excellent stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2598–2605, 2005     

Small-angle neutron scattering study of concentrated colloidal dispersions: the interparticle interactions between sterically stabilized particles

Small-angle neutron scattering (SANS) was used to investigate the interparticle interactions in concentrated dispersions of colloidal silica stabilized either by steric or by electrostatic repulsive interactions. In 10 mM NaCl, an adsorbed PEO layer is required to prevent flocculation, and particles are stabilized by steric repulsions. The adsorbed layer was made invisible to neutrons by contrast matching with the aqueous continuous phase. Dispersions of the same particles at the same concentrations but in the absence of added salt and adsorbed PEO were also studied. In both cases, the SANS spectra of concentrated dispersions show a peak at low Q, which is due to interparticle interactions: a structure factor. The SANS data can be described rather well by a homogeneous spherical form factor and a structure factor based on the Hayter-Penfold/Yukawa potential model. The steric potential was compared to the electrostatic potential obtained by fitting the SANS data of the bare silica dispersions. The steric potential shows a greater dependence on the particle volume fraction, which we ascribe to the penetration and compression of the adsorbed PEO layer as the particles approach.     

Protein–polysaccharide associative interactions in the design of tailor-made colloidal particles

This article reviews some recent advances in the use of diverse protein–polysaccharide associative interactions in the design of colloidal particles having potential to be used for both fortification of food colloids with health-promoting bioactive compounds with better control of their physical stability and breakdown within the gastrointestinal tract. Protein–polysaccharide associative interactions are discussed in the following aspects: (i) the formation of micro- and nanoparticles for the delivery of health promoting ingredients (nutraceuticals); (ii) the controlled gastrointestinal fate of colloidal particles; (iii) the formation of biopolymer-based particles as fat replacers; and (iv) the behavior of colloidal particles as stabilizers of emulsions and foams. The first aspect concerns soluble protein–polysaccharide complex particles (electrostatic nanocomplexes, complex coacervates, covalent conjugates), mixed hydrogel particles, and nanoemulsion-based delivery systems.     

Steric and bridging interactions between two plates induced by grafted polyelectrolytes

If colloidal particles are grafted with a polymer, then the grafted chains can provide steric repulsion between them. If some of the grafted polymer chains are also adsorbed to a second particle, then a bridging force is generated as well. For uncharged plates and polymer, the following contributions to the free energy of the system have been taken into account in the calculation of the interaction force: (i) the Flory-Huggins expression for the mixing free energy of the grafted chains with the liquid; (ii) the entropy loss due to the connectivity of the polymeric segments; (iii) the van der Waals interactions between the segments and the plates; and (iv) the free energy of adsorption of the polymer segments of the grafted chains on the other plate. For charged plates, the electrostatic free energy as well as the free energy of the electrolyte are included in the total free energy of the system. By minimizing the free energy with respect to the segment concentration and, when it is the case, with respect to the electrical potential, equations for the segment number density distribution and for the electrical potential are obtained, on the basis of which the interactions between two plates grafted with polymer chains that can be also adsorbed on the other plate were calculated. The interaction thus obtained includes steric and bridging forces.     

Self-assembly of poly(N-isopropylacrylamide)-carrying microspheres into two-dimensional colloidal arrays

Droplets containing polymer particles were deposited on a substrate. Poly(N-isopropylacrylamide) (PNIPAM) hydrogel and particles with PNIPAM graft chains on the surface self-assembled into a two-dimensional (2-D) superlattice when their dilute dispersions were dried on substrates. The capillary force between the particles induced ordered array formation during water evaporation. The presence of a PNIPAM layer on the particle surface gave the particles steric stability during ordered array formation. By grafting PNIPAM chains on particle surfaces by living radical polymerization, we successfully controlled the structural patterns of the colloidal arrays. These, controllable, 2-D colloidal arrays were generated on various substrates upon air-drying.     

Flocculation mechanism induced by cationic polymers investigated by light scattering

Three cationic polymers with molecular weights and charge densities of 3.0 x 10(5) g/mol and 10%, 1.1 x 10(5) g/mol and 40%, and 1.2 x 10(5) g/mol and 100% were chosen as flocculants to aggregate silica particles (90 nm), under various conditions, including change in polymer dosage, particle concentration, background electrolyte concentration, and shear rate. The size and structure of flocs produced were determined using the static light scattering technique. On the basis of measurements of polymer adsorption and its effect on the zeta potential and floc properties, it has been found that the polymer charge density plays an important role in determining the flocculation mechanism. Polymers with a 10% charge density facilitate bridging, 40% charged polymers bring about either a combination of charge neutralization and bridging or bridging, depending on the polymer dosage, and polymers with the charge density of 100% induce electrostatic patch flocculation mechanism at the optimum polymer dosage and below but bring about bridging mechanism at the polymer dosage approaching the adsorption plateau value. Bridging aggregation can readily be affected by the particle concentration, and an increase in particle concentration results in the formation of larger but looser aggregates, whereas electrostatic patch aggregation is independent of particle concentration. The addition of a background electrolyte aids in bridging aggregation while it is detrimental to electrostatic patch aggregation. It has also been found that the effect of shear rate on the mass fractal dimension depends on polymer charge density.     

Particle morphology in the radiation-induced heterophase polymerization of vinyl chloride with solvent added in small amounts

Investigations were carried out on the polymer particle morphology obtained in the early stages of radiation-induced bulk polymerization of vinyl chloride with solvent added in small amounts over the temperature range of ?10 to 70°C under quiescent conditions. At low temperatures, when the polymerization is carried out in the absence of solvent, there is flocculation of irregular aggregates of two types depending on polymerization conditions: (i) small primary particles that remain finely dispersed and (ii) large flocs that undergo rapid sedimentation. By addition of increasing amounts of solvent a gradual change towards single small spherical particles that remain finely dispersed is obtained. With more than 3% w/w THF, spherical particles in latexlike dispersions are obtained in polymerizations at ?10 and 22.8°C, and show a small change in size with increasing amounts of THF. In the high-temperature range, 50–70°C, where spherical particles can be obtained in the absence of solvent, no significant changes are produced by addition of THF. The results are discussed in the terms of a marked increase in particle plasticization by the solvent, enabling the coalescence of flocculated particles of small size to occur also in polymerization at low temperature.