Transition from dilute to concentrated electrokinetic behavior in the dielectric spectra of a colloidal suspension

Dielectric spectroscopy is used to measure the complex permittivity of 200 and 100 nm diameter polystyrene latex suspended in potassium chloride (KCl) solutions over the frequency range 10(4)-10(7) Hz as a function of particle volume fraction (?) and ionic strength. Dilute suspension dielectric spectra are in excellent agreement with electrokinetic theory. A volume fraction dependence of the dielectric increment is observed for low electrolyte concentrations (0.01, 0.05, and 0.1 mM) above ? ≈ 0.02. This deviation from the dilute theory occurs at a critical frequency ω* that is a function of volume fraction, particle size, and ionic strength. The dielectric increment of suspensions at the highest salt concentration (1 mM) shows no volume fraction dependence up to ? = 0.09. Values of ω* are collapsed onto a master curve that accounts for the length and time scales of ion migration between neighboring particles. The measured conductivity increment is independent of volume fraction and agrees with theory after accounting for added counterions and nonspecific adsorption.     

Colloidal dispersions of octadecyl grafted silica spheres in toluene: a global analysis of small angle neutron scattering contrast variation and concentration dependence measurements

In this paper we report measurements of the form factor and the structure factor of a sterically stabilized colloidal dispersion consisting of silica spheres coated with octadecane in toluene by small angle neutron scattering (SANS). The phase diagram of this system shows the liquid-liquid coexistence line and also a jamming transition at higher concentrations, where the jamming line intersects the coexistence line roughly at the critical point. We have performed SANS experiments at a temperature well above the transition temperature and at various volume fractions phi, spanning from the very dilute regime (phi=0.2%) to the critical concentration (phi=16%) and the highly viscous regime (phi=39.2%). Except for the very dilute regime, we observe a structure factor S(q) in all other cases. We fitted our data over the whole concentration regime using a global fitting routine with a core-shell model for the form factor P(q), taking into account the structure factor, which we describe with the Robertus model for an adhesive polydisperse core-shell particle. At a volume fraction of phi=5% a SANS contrast variation experiment has been performed. From that the product of the volume of the shell and the amount of solvent within the corona of our core-shell particle could be determined. At the most probable shell thickness of 2.3 nm a solvent content of about 50% within the corona was found. Moreover we could conclude that the core is not interpenetrated by solvent molecules. From the contrast variation experiment followed that the structure factor at zero average contrast exhibits a strong q dependence, which is an effect of an inhomogeneous particle in combination with a size distribution.     

The effect of preparation procedure and composition of water-ethanol suspensions of amorphous silica on their aggregative stability and kinetics of coagulation

The method of flow ultramicroscopy is employed to study the effect of the composition and preparation procedure of dilute water-ethanol suspensions of two samples of amorphous silica (fractionated fused quartz and monodisperse amorphous silica) on the kinetics of their coagulation. It is revealed that all suspensions prepared by the addition of silica powders to water-ethanol mixtures with ethanol contents of 96 and 40 vol % are stable with respect to aggregation, as the suspensions prepared by the addition of aliquots of concentrated dispersions of the aforementioned silica samples in 96% ethanol aged for different time periods to water-ethanol mixtures containing 96 vol % ethanol. At a 40-vol % content of ethanol in the mixture, the coagulation whose character (including “superfast” coagulation) substantially depends on the time of aging of initial concentrated silica dispersions occurs. Furthermore, kinetic studies are performed for the coagulation of dilute silica suspensions prepared by the addition of silica powders to water-ethanol solutions containing 40 vol % of ethanol and traces (<1 ppm) of poly(ethoxysilane), poly(acrylic acid), and a supernatant prepared by the centrifugation of concentrated silica dispersion in 96% ethanol aged for more than 3 months. It is found that the addition of aliquots of the aforementioned ethanol solutions to silica suspensions in 40% ethanol, which are initially stable with respect to aggregation, causes their superfast coagulation.     

Coagulation and flocculation measurements by photon correlation spectroscopy — colloidal SiO2 bare and covered by polyethylene oxide

With photon correlation spectrometry (PCS) the diffusion coefficients, average diameters and polydispersities of colloidal particles can be determined in dilute aqueous suspensions. In this study PCS is used to follow the coagulation and flocculation of silica particles. Electrolyte solution added to suspensions of bare particles and of particles covered with adsorbed polyethylene oxide layers induces aggregation. The rate constants of aggregation are evaluated by the second-order Smoluchowski theory with the assumptions of spherical aggregated particles and volume proportional light-scattering amplitude. Adsorbed PEO layers of molar mass lower thanM _w=160000 decrease the critical flocculation concentration and the flocculation states and rate constants for bare and covered particles are the same at high electrolyte concentrations. Polymer layers of high molar mass (M _w=325000, 900000) reducved at full coverage the rate constants and stabilize the suspensions even at high electrolyte concentrations. At low coverage adsorption of high molar mass polymers results in the same values as of low molar mass PEO. The correlation between rate constants and hydrodynamic PEO layer thicknesses demonstrates the steric influence of the tails of the adsorbed macromolecules on stability and flocculation.Dedicated to Prof. Dr. Joachim Klein on the occasion of his 60th birthday     

The Effect of Composition of Water–Ethanol Solutions on the Kinetics of Coagulation of Fused Quartz Suspensions

The effect of composition of water–ethanol solutions containing 0–96 vol % alcohol on the coagulation kinetics of dilute fused quartz suspensions is studied using flow ultramicroscopy technique. It is established that, in both water and ethanol containing 4 vol % water, freshly prepared quartz suspensions are stable with respect to aggregation; at ethanol concentrations from 10 to 90 vol %, an ultrafast coagulation takes place, with characteristic time (coagulation period) being essentially smaller compared to a value corresponding to the Smoluchowski theory of fast coagulation kinetics. It was shown that the aging of the aforementioned suspensions for more than 24 h results in slow coagulation at high and low alcohol content, but its ultrafast character is retained in the ethanol concentrations range of 40–48 vol %. The probable reasons for the ultrafast coagulation in the disperse systems specified are discussed.     

Linear Viscoelastic Behavior of Multiphase Dispersions

The linear viscoelastic behavior of polymer-thickened oil-in-water emulsions, polymer-thickened solids-in-liquid suspensions, and their blends is investigated using a controlled-stress rheometer. The emulsions exhibit a predominantly viscous behaviour at low values of oil concentration in that the loss modulus (G") exceeds the storage modulus (G') over most of the frequency range. At high values of oil concentration, the emulsions exhibit a predominantly elastic behavior. The ratio of storage modulus to loss modulus (G'/G") increases with the increase in oil concentration. Emulsions follow the theoretical model of J. F. Palierne (1990, Rheol. Acta 29, 204) only at low values of oil volume fraction (/=G' over most of the frequency range. The ratio G'/G" varies only slightly with the increase in solids volume fraction. The Palierne model describes the linear viscoelastic properties of suspensions accurately only at low values of solids volume fraction. At high values of solids concentration, the Parlierne model underpredicts the linear viscoelastic properties of suspensions and the deviation increases with the increase in solids concentration. The blends of emulsions and suspensions exhibit strong synergistic effects at low to moderate values of frequencies; the plots of blend modulus versus emulsion content exhibit a minimum. However, at high values of frequency, the blend modulus generally falls between the moduli of pure suspension and pure emulsion. The high-frequency modulus data of blends of emulsions and suspensions are successfully correlated in terms of the modulus ratio versus volume fraction of solids, where modulus ratio is defined as the ratio of blend modulus to pure emulsion modulus at the same frequency. Copyright 2000 Academic Press.     

The Effect of Composition of Water-Ethanol Solutions on Coagulation Kinetics of Amorphous Monodisperse Silica Suspensions

The effect of the composition of water-ethanol solutions on the coagulation kinetics of dilute amorphous monodisperse silica suspensions is studied using flow ultramicroscopy technique. It is found that the suspensions prepared by the addition of an aliquot of concentrated and stored for more than 20 days suspension of the aforementioned silica in 96% ethanol to water-ethanol mixtures containing 96–80 vol % of ethanol are stable with respect to aggregation. A decrease in the alcohol concentration in a system leads to an ultrafast coagulation, whose characteristic time (coagulation period) is much smaller than the value corresponding to the Smoluchowski theory of fast coagulation. It is established that the highest coagulation rate is observed for the suspensions containing 40 vol % of ethanol. Mechanisms of the aggregation stability and ultrafast coagulation of the studied suspensions are discussed.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 475–478.Original Russian Text Copyright © 2005 by Zhukov, Zavarovskaya, Chernoberezhskii.     

Adsorption behavior of oxyethylated surfactants at the air/water interface

The low-shear viscosity eta(0) of colloidal suspensions of acrylic latex or silica in aqueous gelatin has been measured at a temperature above the sol-gel transition. Measurements were made on dilution of a concentrated suspension with water or a gelatin solution. Thus, either the gelatin : colloid ratio was maintained or it was varied at constant aqueous gelatin concentration. Systems were studied with four lime-processed gelatins of different molecular weights at two concentrations of added salt. In addition, the latex particle size and the thickness of the adsorbed gelatin layer were measured by photon correlation spectroscopy (PCS) under dilute conditions. The dependence of the low-shear viscosity eta(0) on particle concentration was exponential and did not follow the well-established Krieger-Dougherty model for simple hard-sphere suspensions over the concentration range studied. A simple phenomenological model, eta(0)=eta(o)10(phi(e)/phi(s)), was found to predict the behavior well. Here, eta(o) is the viscosity of a gelatin solution of the corresponding solution concentration, phi(e) is proportional to the volume fraction of the particles, and phi(s) is a scaling factor, which was determined to have a value of 0.85. With this value of phi(s), the dimensions determined from PCS could be used to predict the viscosity values.     

Dielectric relaxation behavior of colloidal suspensions of palladium nanoparticle chains dispersed in PVP/EG solution

Dielectric measurements were carried out on colloidal suspensions of palladium nanoparticle chains dispersed in poly(vinyl pyrrolidone)/ethylene glycol (PVP/EG) solution with different particle volume fractions, and dielectric relaxation with relaxation time distribution and small relaxation amplitude was observed in the frequency range from 10(5) to 10(7) Hz. By means of the method based on logarithmic derivative of the dielectric constant and a numerical Kramers-Kronig transform method, two dielectric relaxations were confirmed and dielectric parameters were determined from the dielectric spectra. The dielectric parameters showed a strong dependence on the volume fraction of palladium nanoparticle chain. Through analyzing limiting conductivity at low frequency, the authors found the conductance percolation phenomenon of the suspensions, and the threshold volume fraction is about 0.18. It was concluded from analyzing the dielectric parameters that the high frequency dielectric relaxation results from interfacial polarization and the low frequency dielectric relaxation is a consequence of counterion polarization. They also found that the dispersion state of the palladium nanoparticle chain in PVP/EG solution is dependent on the particle volume fraction, and this may shed some light on a better application of this kind of materials.     

Rheology of binary colloidal structures assembled via specific biological cross-linking

The selectivity and range of energies offered by specific biological interactions serve as valuable tools for engineering the assembly of colloidal particles into novel materials. In this investigation, high affinity biological interactions between biotin-coated "A" particles (RA = 0.475 microm) and streptavidin-coated "B" particles (RB = 2.75 microm) drive the self-assembly of a series of binary colloidal structures, from colloidal micelles (a large B particle coated by smaller A particles) to elongated chain microstructures (alternating A and B particles), as the relative number of small (A) to large (B) particles (2 < or = NA/NB < or = 200) is decreased at a low total volume fraction (10(-4) < or = phiT < or = 10(-3)). At a significantly higher total volume fraction (phiT > or = 10(-1)) and a low number ratio (NA/NB = 2), the rheological behavior of volume-filling particle networks connected by streptavidin-biotin bonds is characterized. The apparent viscosity (eta) as a function of the shear rate gamma, measured for networks at phiT = 0.1 and 0.2, exhibits shear-rate-dependent flow behavior, and both the apparent viscosity and the extent of shear thinning increase upon an increase of a factor of 2 in the total volume fraction. Micrographs taken before and after shearing show a structural breakdown of the flocculated binary particle network into smaller flocs, and ultimately a fluidlike suspension, with increasing shear rate. Rheological measurements provide further proof that suspension microstructure is governed by specific biomolecular interactions, as control experiments in which the streptavidin molecules on particles were blocked displayed Newtonian flow behavior. This investigation represents the first attempt at measuring the rheology of colloidal suspensions where assembly is driven by biomolecular cross-linking.     

Coupling between polymer adsorption and colloidal particle aggregation

Studies of the adsorption of high molecular weight polymers on colloidal latex and silica particles and their subsequent flocculation were carried out. Neutral polyethylene oxide samples with both a narrow and a broad molecular weight distribution were used together with low charged cationic copolymers. The influence of the particle concentration and polymer dose on the flocculation were systematically investigated under quiescent conditions.Equilibrium bridging only occurred with polyelectrolyte, even in very dilute suspensions, at high particle coverage. In contrast to this, non-equilibrium bridging occurred with both neutral polymer and polyelectrolytes but only for more concentrated suspensions and small amounts of adsorbed polymer. Polymer adsorption in dilute suspensions, which did not show particle aggregation was measured an electrophoretic technique. In more concentrated suspensions, where flocculation takes place, we found that aggregation prevents further polymer adsorption and induces both an excluded volume and a surface effect. The consequences on the shape of the isotherms differ according to the aggregation mechanism.A significant decrease of the amount, , of adsorbed polymer is observed with non-equilibrium bridging. When both mechanisms simultaneously contribute to the aggregation, the value of depends on their relative importance. In the intermediate range of copolymer dose their respective contributions are critically sensitive to the details of the mixing step and stirring, leading to non reproducible experimental results.     

Latex-particle-stabilized emulsions of anti-Bancroft type

Here, we investigate water-in-oil (W/O) emulsions that are stabilized by polystyrene latex particles with sulfate surface groups. The particles, which play the role of emulsifier, are initially contained in the disperse (water) phase. The existence of such emulsions formally contradicts the empirical Bancroft rule. Theoretical considerations predict that the drop diameter has to be inversely proportional to the particle concentration, but should be independent of the volume fraction of water. In addition, there should be a second emulsification regime, in which the drop diameter is determined by the input mechanical energy during the homogenization. The existence of these two regimes has been experimentally confirmed, and the obtained data agree well with the theoretical model. Stable W/O emulsions have been produced with hexadecane and tetradecane, while, in the case of more viscous and polar oils (soybean and silicone oil), the particles enter into the oily phase, and Pickering emulsions cannot be obtained. The formation of stable emulsions demands the presence of a relatively high concentration of electrolyte that lowers the electrostatic barrier to particle adsorption at the oil-water interface. Because the attachment of particles at the drop surfaces represents a kind of coagulation, it turns out that the Schulze-Hardy rule for the critical concentration of coagulation is applicable also to emulsification, which has been confirmed with suspensions containing Na(+), Mg(2+), and Al(3+) counterions. The increase of the particle and electrolyte concentrations and the decrease of the volume fraction of water are other factors that facilitate emulsification in the investigated system. To quantify the combined action of these factors, an experimental stability-instability diagram has been obtained.     

Synthesis and characterization of cubic cobalt oxide nanocomposite fluids

Narrow size distribution cubic Co₃O₄ nanoparticles were synthesized and rheological properties of suspensions of the cubes in oligomeric polyethylene glycol (PEG) were explored over a range of particle volume fractions and rotational shear flow conditions. At low and high particle volume fractions, the relative viscosity of the suspensions is described by a Krieger–Dougherty formula with an intrinsic viscosity consistent with expectations for suspensions of ideal cuboids. At intermediate to high particle loadings, the suspensions manifest complex rheological behavior, including shear thinning and shear-thickening features. These observations are discussed in terms of the charge carried by the cubes and the shear rate/volume fraction dependency of the transition from shear thinning to shear thickening.     

Rheology of polystyrene latexes with adsorbed and free gelatin

The rheology of monodisperse polystyrene latex particles of two different particle radii (26 and 67 nm) has been studied with a range of concentrations of the polyampholyte gelatin. Gelatin contributes to the rheology by adsorption to the particles and by thickening the continuous phase. High viscosities and strong shear thinning are measured for low volume fractions of latex. A procedure is presented to deconvolute the effects of free and bound gelatin by applying simple hard-sphere models. This procedure allows us to estimate the effective size of the gelatin-covered particles as well as the continuous-phase gelatin concentration and viscosity. The layer thicknesses from rheology agree well with those from PCS. The effect of varying particle volume fraction, ionic strength, pH and gelatin and surfactant concentration on the rheology of these suspensions is presented. For the smaller latex, the adsorbed layer occupies a greater fraction of the effective volume. Increasing free polymer concentration reduces the adsorbed-layer thickness. The reduced critical shear stress increases with the suspension viscosity for suspensions of the 26 nm latex but is constant for the 67 nm latex. At very high shear (>2000 s⁻¹), the suspensions show excess shear thinning over that expected from a hard-sphere model. This excess thinning is attributed to deformation of the adsorbed gelatin layer under high shear stress and interpreted in terms of an empirical interparticle potential.     

Protein Adsorption onto Zirconia Modified with Terminally Grafted Polyvinylpyrrolidone

Electroacoustics was used to study SDS-stabilized sunflower oil-in-water emulsions, with oil volume fractions between 2% and 50%. The dynamic mobility of the oil droplets was measured; the size and electric charge on the drops were calculated using formulas derived for dilute and concentrated systems and the results were compared. The relation derived for concentrated systems appears to be valid up to at least 50% provided the particles remain within the size range of the instrument, which shifts upward with rising concentration. Conductivity and pH had little effect on particle properties in the range studied; higher oil volume fraction (φ) had a substantial influence on the particle size produced in a homogenizer, but not on the zeta potential. Both median size and spread decreased with increases in φ. In contrast, both size and charge were hardly affected at volume fractions less than 10%. Dilution of the emulsion with a surfactant solution of the same composition as the water phase changed neither the particle size nor the zeta potential. The temperature of the emulsification process had a significant influence on the particle size but the zeta potential was hardly affected. Surfactant concentration had some effect on size at low volume fractions but not for φ>10%. The electroacoustic method hence could be applied to analyze both the dilute and the concentrated emulsions directly. Copyright 2001 Academic Press.     

Transport of nanoscale latex spheres in a temperature gradient

We use a micrometer-scale optical beam deflection technique to measure the thermodiffusion coefficient D(T) at room temperature (approximately 24 degrees C) of dilute aqueous suspensions of charged polystyrene spheres with different surface functionalities. In solutions with large concentrations of monovalent salts, < or approximately = 100 mM, the thermodiffusion coefficients for 26 nm spheres with carboxyl functionality can be varied within the range -0.9 x 10(-7) cm2 s(-1) K(-1) < D(T) < 1.5 x 10(-7) cm2 s(-1) K(-1) by changing the ionic species in solution; in this case, D(T) is the product of the electrophoretic mobility mu(E) and the Seebeck coefficient of the electrolyte, S(e) = (Q(C)* - Q(A)*)/2eT, D(T) = -S(e) mu(E), where and are the single ion heats of transport of the cationic and anionic species, respectively. In low ionic strength solutions of LiCl, < or approximately = 5 mM, and particle concentrations < or approximately = 2 wt %, D(T) is negative, independent of particle concentration and independent of the Debye length; D(T) = -0.73 +/- 0.05 x 10(-7) cm2 s(-1) K(-1).     

Electrical Conductivity of a Concentrated Suspension of Spherical Colloidal Particles

A general expression for the electrical conductivity of a concentrated suspension of spherical colloidal particles is obtained for the case where the particle zeta potential is low and the overlapping of the electrical double layers of adjacent particles is negligible by using Kuwabara's cell model. It is shown how the conductivity of a concentrated suspension depends on the particle volume fraction, the zeta potential zeta, and the reduced particle radius kappaa (kappa = Debye-Hückel parameter and a = particle radius). It is also found that the obtained conductivity formula tends to Maxwell's formula for two different extreme cases: (i) when the particles are uncharged (zeta = 0) and (ii) when the electrical double layers around the particles are infinitesimally thin (kappaa --> infinity). That is, in the latter limiting case (kappaa --> infinity), the conductivity becomes independent of the zeta potential, just as in the case of dilute suspensions. Copyright 1999 Academic Press.     

Diffusing-wave spectroscopy and interferometry

Diffusing-wave spectroscopy and interferometry, the extensions of dynamic light scattering to materials which exhibit a very high degree of multiple scattering, have been used to measure the early-time, short length scale motion of Brownian particles. The transition from “ballistic” to “diffusive” motion is observed. In very dilute samples, this transition is described very well by theories which explicitly account for the time-dependent hydrodynamic interaction between a Brownian particle and the surrounding fluid. For particle volume fractions exceeding a few per cent, the data deviate from the theory for dilute suspensions, but exhibit a remarkable scaling with the suspension viscosity.