Combined effects of Ca2+ and humic acid on colloid transport through porous media

We report the separate and combined effects of humic acid and Ca²⁺ ions on the transport of colloidal particles through a sand-packed column. Polystyrene latex particles with a sulfate functional group were used as model colloids. The concentrations of both the inlet solution and the effluent solutions were measured during each experimental run. Breakthrough curves were obtained by taking the ratios of each effluent sample concentration to the inlet solution concentration. In the absence of humic acid, the results indicate that increasing the concentration of Ca²⁺ increases particle attachment to the sand, thus causing decreased transport rates of latex particles through the porous bed matrix. Once 4 mg/l humic acid was added to the system, changes were observed in the effect that Ca²⁺ has on latex particle breakthrough. In a system containing calcium, increasing the humic acid concentration was shown to reduce particle attachment and increase transport rates. In the absence of calcium, the ratios for the outlet-to-inlet concentrations were similar for each concentration of humic acid. The electrophoretic mobility was also measured in order to determine the role of electrostatic repulsion in the latex particle transport. The electrophoretic mobility of the latex particles was found to be dependent on humic acid concentration in the absence of Ca²⁺ but not in its presence. Received: 2 February 2001 Accepted: 6 2001     

Cationic and anionic poly(N-isopropylacrylamide) based submicron gel particles: electrokinetic properties and colloidal stability

A cationic and an anionic poly(N-isopropylacrylamide) (poly(NIPAM)) microgel latex were synthesized via batch radical polymerization under emulsifier-free conditions. The hydrodynamic properties, colloidal stability, and electrokinetic characteristics of these two samples were studied. The hydrodynamic particle size variation was discussed by considering the effect of salinity and temperature on the shrinkage of the thermally sensitive polymer domains. The colloidal stability also depended on temperature and electrolyte concentration. A stability diagram with two well-defined domains (stable and unstable) was obtained. The flow from one domain to the other was fully reversible due to the peculiar (de)hydration properties of the polymer. The electrokinetic behavior, which depends on electrical and frictional properties of the particles, was analyzed via electrophoretic mobility measurements. Results were discussed by considering both the particle structure dependence on temperature and salinity, and the electric double layer compression. In addition, the electrophoretic mobility data were analyzed using Ohshima's equations for particles covered by an ion-penetrable surface charged layer, as well as using another simpler equation for charges located on a hydrodynamic equivalent hard sphere. Differences between the properties of both latexes were justified by the presence of a hydrophilic comonomer, aminoethyl methacrylate hydrochloride (AEMH), in the cationic microgel.     

The electrokinetic properties of latex particles: comparison of electrophoresis and dielectrophoresis

A comprehensive study of the AC and DC electrokinetic properties of submicrometre latex particles as a function of particle size and suspending medium conductivity and viscosity is presented. Electrophoretic mobility and dielectrophoretic cross-over results were measured for particle diameters ranging from 44 to 2000 nm. The zeta potentials of the particles were calculated from the electrophoretic mobility data for different suspending medium conductivities, using various models, with and without the inclusion of surface conduction. The dielectrophoretic data was analysed to derive values for the Stern layer conductance and zeta potentials.     

Startup of electrophoresis in a suspension of colloidal spheres

The transient electrophoretic response of a homogeneous suspension of spherical particles to the step application of an electric field is analyzed. The electric double layer encompassing each particle is assumed to be thin but finite, and the effect of dynamic electroosmosis within it is incorporated. The momentum equation for the fluid outside the double layers is solved through the use of a unit cell model. Closed‐form formulas for the time‐evolving electrophoretic and settling velocities of the particles in the Laplace transform are obtained in terms of the electrokinetic radius, relative mass density, and volume fraction of the particles. The time scale for the development of electrophoresis and sedimentation is significantly smaller for a suspension with a higher particle volume fraction or a smaller particle‐to‐fluid density ratio, and the electrophoretic mobility at any instant increases with an increase in the electrokinetic particle radius. The transient electrophoretic mobility is a decreasing function of the particle volume fraction if the particle‐to‐fluid density ratio is relatively small, but it may increase with an increase in the particle volume fraction if this density ratio is relatively large. The particle interaction effect in a suspension on the transient electrophoresis is much weaker than that on the transient sedimentation of the particles.     

Electrophoretic mobility of latex particles: effect of particle size and surface structure

The influence of particle size on the electrophoretic mobility of negatively charged latex particles was examined by a comparison between theory and experiment. Theoretical values for the dependence of the mobility on electrolyte concentration were calculated by a modified White–O’Brian model (Hidalgo-Alvarez et al., Adv. Coll. Interf. Sci. 67 (1996) 1) which enables the consistent calculation of the zeta (ζ) potential. For three polystyrene latexes of different size but similar surface charge density the measured mobilities increased with increasing radius for the electrolyte range under consideration. The theoretical calcalations resulted in a qualitatively correct prediction of the experimental data. The experimental comparison of the mobilities of hydrophobic and hydrophilic particles of similar size and surface charge density lead to the conclusion that hydrophilic surfaces lower the electrophoretic mobility. The same theoretical model was able to describe correctly this observed behavior by assuming a greater distance of the plane of shear. The effect of a spatial distribution of the charges was examined by characterizing an electrosterically stabilized latex. Contrary to all standard latices with surface charges this latex didn't show any mobility maximum as a function of electrolyte concentration.     

Separation and characterization of sub-microm- and microm-sized particles by capillary zone electrophoresis

The analytical separation and characterization of particles in the size range of sub-microm and microm diameters by capillary zone electrophoresis (CZE) has been reviewed. The theoretical basis, on which the mobility can be interpreted to provide information regarding characteristics of particle surface, has shortly been presented. Particular emphasis was put on the model dependence of that interpretation and the need in most applications to forego the classical idealized model of spherical particles with "smooth" surfaces and to apply more realistic models, which take the "hairy" surface of real particles into account. Some highlights of the literature on the CZE of polystyrene latex microspheres, organic and inorganic colloids, lipoprotein particles, viruses, liposomes, biological membrane vesicles, and biological cells have been discussed. Also summarized are the reports on the particle size dependence of mobility and peak broadening in CZE and on electrophoretic behavior of rodlike particles and particle aggregates. Finally, the effects of neutral polymers in the background electrolyte on particle mobility and peak width are reviewed.     

The effect of acrylic acid amount on the colloidal properties of polystyrene latex

Poly(styrene-co-acrylic acid) (St/AA) latices were prepared by using a batch soap-free emulsion copolymerisation in non-buffered medium. Polymerisation kinetics, followed by gravimetric method, revealed that increasing AA comonomer concentration was directly proportional to the copolymerisation rate, while adding AA comonomer caused a strong decrease of particle size of final St/AA latex particle without affecting the size distribution. Transmission electron microscopy indicated that the particles were monodispersed and spherical in shape irrespective of AA amount used in the investigated range. The colloidal stability of the latices was increased upon increasing the AA concentration; owing to the electrosteric stabilisation originated from AA-rich layer on the particle surface. In addition, electrophoretic mobility of formed particles versus polymerisation conversion exhibited the constancy of the surface charge density during the polymerisation process and was inferred for discussion of the polymerisation mechanism of this system.     

Polymer mediated peptide immobilization onto amino-containing N-isopropylacrylamide-styrene core-shell particles

Monodisperse cationic core-shell latex particles have been prepared using a shot polymerization process, with N-(3-aminopropyl)-methacrylamide-hydrochloride (APMH) as the functional monomer. The final latexes were characterized with respect to final polymerization conversion, water soluble polymer formation, particle size and size distribution, surface charge density and electrokinetic properties. Then the covalent grafting of maleic anhydride-alt-methyl vinyl ether (MAMVE) copolymer onto aminated latex particles was investigated. The most efficient conditions to obtain derivatised particles with no alteration of the colloidal stability were to control both polymer amount/latex particles concentration ratio and the mixing method of the two species. The charge inversion of the hydrolysed MAMVE functionalized particles was demonstrated by measuring the electrophoretic mobility as a function of pH. Finally, the covalent binding approach was implemented with peptide-MAMVE conjugates, confirming the great potential of this promising methodology for the preparation of reactive latex particles bearing peptides.     

Collaborative studies of zeta-potential measurements and electrophoretic measurements using reference sample

Simultaneous measurements of zeta-potential for two standard latex suspensions were carried out so as to assess the reliability of each of these measurement techniques and find means for their improvement. Furthermore, syntheses of a reference particle dispersion stabilized sterically in an aqueous medium without any electrostatic effects and measurements of zeta-potential using the reference dispersion as a standard were performed under various experimental conditions. It became apparent that the dense adsorption layer of hydroxypropylcellulose (HPC), with a lower critical solution temperature (LCST), formed on latex particles with a low surface charge density at temperatures higher than the LCST, plays a role in completely shielding the electrostatic effect arising from the surface charge on the bare particles. Such reference particles with zero zeta-potential allow us to determine the electrophoretic mobility of unknown samples at the one-half depth in the electrophoretic cell by subtracting the mobility of the reference sample at the same level. Furthermore, the zeta-potential of the cell wall can be easily determined from the mobility of the reference sample, because the apparent velocity profile of the reference sample indicates the liquid flow velocity in the cell.     

The effect of metallic cations on the electrophoretic properties of a pretreatedHevea latex

High-ammonia latex concentrate prepared from doubly-centrifuged fieldHevea latex was exhaustively dialysed to remove any residual water-soluble non-rubber constituents. The electrophoretic mobilities of the dialysed latex in the presence of various metallic cations were investigated as a function of electrolyte concentration. The mobility decreased with increasing concentration of the cations Na⁺, Ba²⁺, Mg²⁺ and Ca²⁺ in a manner consistent with the effect of simple electrolyte on compression of the electric double layer. Anomalous behaviour was noted for the divalent ion copper, in that it reversed the charge of the latex particles at a concentration even lower than that of uranyl ions. Multivalent cations (lanthanum, cerium and thorium) had a profound influence on the latex particles where very low charge reversal concentrations were observed. It is believed that strong adsorption of hydrolysed species from the metallic ions was responsible for reversing the charge of the originally negative latex particles. These experiments indicated that the efficiency with which the cations reversed the charge of the latex particle surface was in the order: lanthanum > cerium > copper > thorium > uranyl > calcium > magnesium > barium > sodium. The number of cation binding sites on the latex particle surface and the chemical free energies of cation adsorption were calculated. It was found that the interaction of the latex particle with the hydrolysable metallic cations was much more stronger than that with the simple divalent cations and that this intercation was comparable to that of biological surfaces.     

Mechanisms of fibrinogen adsorption on latex particles determined by zeta potential and AFM measurements

The adsorption of fibrinogen on polystyrene latex particles was studied using the concentration depletion method combined with the AFM detection of residual protein after adsorption. Measurements were carried out for a pH range of 3.5-11 and an ionic strength range of 10(-3)-0.15 M NaCl. First, the bulk physicochemical properties of fibrinogen and the latex particle suspension were characterized for this range of pH and ionic strength. The zeta potential and the number of uncompensated (electrokinetic) charges on the protein were determined from microelectrophoretic measurements. It was revealed that fibrinogen molecules exhibited amphoteric characteristics, being on average positively charged for pH <5.8 (isolectric point) and negative otherwise. However, the latex particles did not show any isoelectric point, remaining strongly negative for this pH range. Afterward, systematic measurements of the electrophoretic mobility of fibrinogen-covered latex were carried out as a function of the amount of adsorbed protein, expressed as the surface concentration. A monotonic increase in the electrophoretic mobility (zeta potential) of the latex was observed in all cases, indicating a significant adsorption of fibrinogen on latex for pH below 11. It was also proven that fibrinogen adsorption was irreversible, with the maximum surface concentration varying between 2.5 and 5 × 10(3) μm(-2) (weight concentration of a bare molecule was 1.4 to 2.8 mg m(-2)). These measurements revealed two main adsorption mechanisms of fibrinogen: (i) the unoriented (random) mechanism prevailing for lower ionic strength, where adsorbing molecules significantly penetrate the fuzzy polymeric layer on the latex core and (ii) the side-on adsorption mechanism prevailing for pH > 5.8 and a higher ionic strength of 0.15 M. It was also shown that in the latter case, variations in the zeta potential with the protein coverage could be adequately described in terms of the electrokinetic model, previously formulated for planar substrate adsorption. On the basis of these experimental data, an efficient procedure of preparing fibrinogen-covered latex particles of controlled monolayer structure and coverage was envisaged.     

Synthesis of amino‐functionalized latex particles by a multistep method

Cationic latex particles with surface amino groups were prepared by a multistep batch emulsion polymerization. In the first one or two steps, monodisperse cationic latex particles to be used as the seed were synthesized, and in the third step, two different amino‐functionalized monomers [aminoethylmethacrylate hydrochloride (AEMH) and vinylbenzylamine hydrochloride (VBAH)] were used to synthesize the final functionalized latex particles. 2,2′‐Azobisisobutyramidine dihydrochloride was used as the initiator, and different concentrations of two quaternary ammonium emulsifiers with hydrophobic chains of different lengths were examined. To characterize the final latexes yields were obtained gravimetrically, and particle size distributions and average particle diameters were determined by transmission electron microscopy and photon correlation spectroscopy. The amount of amino groups was determined by fluorimetry. The effect of the amino‐functional monomer used on the final latexes and the colloidal behavior of the system were studied. The influence of the different conditions utilized to synthesize the latexes on the colloidal stability of the particles was evaluated in terms of the Fuchs stability ratio and electrophoretic mobility. High yields of the amino‐functional monomers were obtained. Surface amino, amidine, and quaternary ammonium groups provided the cationic character. The colloidal stability behavior of the products obtained was compatible with their cationic character. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2929–2936, 2001     

Effects of trace water on charging of silica particles dispersed in a nonpolar medium

This paper presents an investigation of the effects of trace water on the charging of silica (SiO(2)) particles dispersed in a nonpolar medium. There are a growing number of applications that seek to use electrostatic effects in apolar media to control particle movement and aggregation stability in such systems. One factor that is often overlooked in the preparation of nonpolar colloidal dispersions is the amount of water that is introduced to the system by hygroscopic particles and surfactants. The amount and location of this water can have significant effects on the electrical properties of these systems. For nonpolar surfactant solutions it has been shown that water can affect the conductivity, and it has been speculated that this is due to swelling of the polar cores of inverse micelles, increasing the fraction of them that are charged. Some studies have suggested that particle surface charging may also be sensitive to water content, but a clear mechanism for the process has not been fully developed. The situation with particles is further complicated by the fact that it is often unclear whether the water resides on the particle surfaces or in the polar cores of inverse micelles. The current work explores not only the effect of water content on reverse micelle and particle charging but seeks to differentiate between water bound to the particles and water located in the micelles. This is accomplished by measuring the solution conductivity and the electrophoretic mobility of silicon dioxide particles dispersed in solutions of Isopar-L and OLOA 11000. The water content is determined for both the dispersion and the supernatant after centrifuging the particles out. It is found that at equilibrium the majority of the water in the system adsorbs to the surface of the hygroscopic silica particles. In addition, the effect of water on particle electrophoretic mobility is found to be dependent on surfactant concentration. At small OLOA concentrations, additional water results in an increase in particle mobility due to increased particle charging. However, at large OLOA concentrations, additional water leads to a decrease in particle mobility, presumably as a result of increased electrostatic screening or neutralization. Thus, particle charging and electrophoretic mobility in an apolar surfactant solution are found to be highly sensitive to both the total water content in the system and to its concentration relative to the amount of surfactant present.     

Transient electrophoresis in a suspension of charged particles with arbitrary electric double layers

The startup of electrophoretic motion in a suspension of spherical colloidal particles, which may be charged with constant zeta potential or constant surface charge density, due to the sudden application of an electric field is analytically examined. The unsteady modified Stokes equation governing the fluid velocity field is solved with unit cell models. Explicit formulas for the transient electrophoretic velocity of the particle in a cell in the Laplace transforms are obtained as functions of relevant parameters. The transient electrophoretic mobility is a monotonic decreasing function of the particle-to-fluid density ratio and in general a decreasing function of the particle volume fraction, but it increases and decreases with a raise in the ratio of the particle radius to the Debye length for the particles with constant zeta potential and constant surface charge density, respectively. On the other hand, the relaxation time in the growth of the electrophoretic mobility increases substantially with an increase in the particle-to-fluid density ratio and with a decrease in the particle volume fraction but is not a sensitive function of the ratio of the particle radius to the Debye length. For specified values of the particle volume fraction and particle-to-fluid density ratio in a suspension, the relaxation times in the growth of the particle mobility in transient electrophoresis and transient sedimentation are equivalent.     

Electrophoresis and electric conduction in a salt-free suspension of charged particles

The electrophoresis and electric conduction of a suspension of charged spherical particles in a salt-free solution are analyzed by using a unit cell model. The linearized Poisson-Boltzmann equation (valid for the cases of relatively low surface charge density or high volume fraction of the particles) and Laplace equation are solved for the equilibrium electric potential profile and its perturbation caused by the imposed electric field, respectively, in the fluid containing the counterions only around the particle, and the ionic continuity equation and modified Stokes equations are solved for the electrochemical potential energy and fluid flow fields, respectively. Explicit analytical formulas for the electrophoretic mobility of the particles and effective electric conductivity of the suspension are obtained, and the particle interaction effects on these transport properties are significant and interesting. The scaled zeta potential, electrophoretic mobility, and effective electric conductivity increase monotonically with an increase in the scaled surface charge density of the particles and in general decrease with an increase in the particle volume fraction, keeping each other parameter unchanged. Under the Debye-Hückel approximation, the dependence of the electrophoretic mobility normalized with the surface charge density on the ratio of the particle radius to the Debye screening length and particle volume fraction in a salt-free suspension is same as that in a salt-containing suspension, but the variation of the effective electric conductivity with the particle volume fraction in a salt-free suspension is found to be quite different from that in a suspension containing added electrolyte.     

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).     

Electrophoretic mobility of a cylindrical colloidal particle in a salt-free medium

Approximate expressions are derived for the electrophoretic mobility of dilute cylindrical colloidal particles in a salt-free medium containing only counterions. The cylinder is assumed to be infinitely long. It is shown that as in the case of a spherical particle, there is a certain critical value of the particle surface charge separating two cases. When the particle surface charge is lower than the critical value (case 1), the electrophoretic mobility increases with increasing particle surface charge per unit length. When the particle surface charge is higher than the critical value (case 2), the mobility becomes constant (for a cylinder in a transverse field) or the increase in the electrophoretic mobility with the particle surface charge becomes suppressed (for a cylinder in a tangential field). These phenomena are caused by the effect of counterion condensation in the vicinity of the particle surface. The critical value of the particle charge is essentially independent of the particle volume fraction phi for the dilute case, unlike the case of a sphere, in which case the critical charge value is proportional to ln(1/phi).     

A new approach to the studies of submicron particle suspensions based on the effect of pressure in capillary zone electrophoresis

A new approach based on the effect of pressure in CZE is suggested for acceleration of particle migration in electrophoretic runs resulting in reduction of the analysis time. It provides conditions for studying fast processes in suspensions. The effect of pressure on the migration of silica spheres with average diameters of 100, 150, and 390 nm was studied by CZE at an applied voltage of 25 kV. The particle hydrodynamic behavior was also investigated under the same capillary dimensions and BGE composition. The total particle mobility (excluding the average flow rate) was found to increase with increasing the pressure applied and particle size. The particle migration mechanism explaining the effect of pressure on particle velocity was shown to be almost the same as in wide‐bore hydrodynamic chromatography. It is based on changing radial distribution of particle concentration along the capillary cross section depending on particle diffusivity. On the basis of this mechanism appearance of a zone of negatively charged particles in electropherograms ahead of the marker peak can be explained.     

Hydrophilic stimuli‐responsive particles for biomedical applications

Hydrophilic and stimuli‐responsive submicronic latex particles based on polyalkyl(meth)acrylamide can be prepared owing to simple radical‐initiated polymerizations in heterogeneous media using a water‐soluble initiator and a crosslinker (methylenebisacrylamide). The paper aims at reviewing the synthesis and properties of functionalized polystyrene‐polyN‐isoprpylacrylamide core‐shell particles or polyN‐isopropylmethacrylamide microgel particles. Particle size of analysis showed that a short nucleation period afforded the synthesis of highly monodispersed latexes. The dramatic change of the colloidal properties (particle size, electrophoretic mobility) was found to reflect the thermal sensitivity of such particles. The hydrophilic nature of the particles below the volume phase transition temperature was found to drastically reduce the physical adsorption of proteins. Some examples of biomedical applications of these stimuli‐responsive particles are briefly reported.     

Colloid Vibration Potential in a Concentrated Suspension of Spherical Colloidal Particles

A relation between the dynamic electrophoretic mobility of spherical colloidal particles in a concentrated suspension and the colloid vibration potential (CVP) generated in the suspension by a sound wave is obtained from the analogy with the corresponding Onsager relation between electrophoretic mobility and sedimentation potential in concentrated suspensions previously derived on the basis of Kuwabara's cell model. The obtained expression for CVP is applicable to the case where the particle zeta potential is low, the particle relative permittivity is very small, and the overlapping of the electrical double layers of adjacent particles is negligible. It is found that CVP shows much stronger dependence on the particle volume fraction φ than predicted from the φ dependence of the dynamic electrophoretic mobility. It is also suggested that the same relation holds between the electrokinetic sonic amplitude of a concentrated suspension of spherical colloidal particles and the dynamic electrophoretic mobility. Copyright 1999 Academic Press.