Charging of Oxide Nanoparticles in Media of Intermediate Dielectric Constant.

The use of surfactants to charge colloidal particles in solvents of intermediate dielectric constants (5 < ε < 40) is investigated. While particle charging mechanisms in aqueous (ε = 80) and apolar (ε < 5) media are well understood, the interplay of these different charging mechanisms, which can all occur in solvents of intermediate dielectric constants (sometimes referred to as "leaky dielectrics"), remains to be fully explored. Conductometric titrations determining the critical micelle concentration (CMC) of the surfactant (aerosol-OT) confirm the existence of reverse micelles in intermediate dielectrics and show that as the solvent dielectric constant decreases, the CMC decreases as well. Electrophoretic mobility measurements of three oxide particles (SiO2, TiO2, and MgO) highlight various charging mechanisms that arise from particle-solvent, particle-surfactant, and solvent-surfactant interactions in a solvent series of alcohols and ketones. The results show that a combination of donor-acceptor particle-solvent interactions, surfactant ion adsorption, and reverse micelle-mediated acid-base interactions can all charge oxide particles in intermediate dielectrics. Furthermore, the results show that the dielectric constant of the solvent affects the relative magnitudes of each charging mechanism.

Effects of Reverse Micellar Structure on the Particle Charging Capabilities of the Span Surfactant Series.

This paper investigates the effects of reverse micellar core size on the particle charging behavior of a series of acidic surfactants in apolar media. A series of Span surfactants was dissolved in deuterated decane at concentrations above the critical micelle concentration. The structures of the reverse micelles were measured using small-angle neutron scattering. It was determined that as the tail length of the surfactant increased, the size of the polar reverse micellar core decreased. Tritailed surfactants formed reverse micelles with the smallest polar cores, with radii of ∼4 Å. The sizes of the polar cores were correlated with the particle charging behavior of the Span surfactant series, as measured in a previous study. It was found that reverse micelles with intermediate core sizes imparted the largest electrophoretic mobilities to the particles. Reverse micelles with very small cores did not offer a large enough polar environment to favor charge stabilization, while very large polar cores favored disproportionation reactions in the bulk, resulting in increased electrostatic screening.

Temperature Effects on Micelle Formation and Particle Charging with Span Surfactants in Apolar Media.

This paper examines the effects of temperature on the micellization and particle charging behavior of the Span surfactant series in an apolar environment. The critical micelle concentrations of each of six surfactants at five temperatures were measured by conductometric techniques. The thermodynamic properties of micellization were calculated using Gibbs-Helmholtz analysis. Magnesia particles were then dispersed in solutions of these surfactants, and their electrophoretic mobilities were measured at three temperatures. Preliminary small-angle neutron scattering (SANS) experiments were conducted to measure the size of aggregates (referred to as reverse micelles) of three of the surfactants. It was found that for all but one of the surfactants the critical micelle concentration (CMC) increased by as much as an order of magnitude across a 40 °C range of temperature. One of the surfactants exhibited a decrease in CMC upon increasing temperature, likely due to a decrystallization of the tails upon reverse micelle formation. The maximum particle mobilities decreased upon increasing temperature due to the increased electrostatic screening by charged reverse micelles at higher temperatures.

Effect of synergists on organic pigment particle charging in apolar media.

The current work investigates the apolar charging behavior of organic pigment particles and the role that synergists play in regard to particle charging. Organic pigments are often used in apolar paints, inks, and most recently electrostatic lithography. For electrolithography to work, the particles must be both stable and possess the correct polarity and magnitude of charge. It is therefore important to better understand the charging behavior and potential charging mechanisms of these particles that have received little or no attention in the literature. Unfortunately, these already complex systems are further complicated by the fact that the stability of organic pigments is often improved through the use of synergists. Synergists are designed to enhance the adsorption of steric stabilizers to the particles. However, their effect on particle charging has not been previously published. In this study, the particle zeta potential is determined for apolar dispersions of magenta and cyan particles in heptane (with and without synergist present). The particles are dispersed with three different surfactants commonly used in apolar charging studies: Span 80, Aerosol-OT, and OLOA 11000. Acid-base interactions appear to play an important role, particularly for cyan. However, due to the complexity of these systems, any general rule must be applied with caution as the particle, surfactant, and synergist chemistry all determine the nature of the particle charge.

Micellization behavior of Aerosol OT in alcohol/water systems.

This paper examines the effects of solvent composition on the micellization behavior of the surfactant Aerosol OT (AOT). The critical micelle concentrations of AOT in the pure solvents methanol, ethanol, propanol, and isopropanol were measured using conductiometric techniques. These solvents were then mixed with water to create solvent spectra from pure alcohol to pure water in 12 increments. Critical micelle concentrations were measured at each solvent composition. Dynamic light scattering was used to verify the presence or absence of micelles in the solvent mixtures. It was found that inverse micelles exist over a range of solvent compositions where εeff < 48 with CMCs increasing with increasing solvent polarity. Micellization was found not to occur when 48 < εeff < 80. Regular micelles formed in pure water, with the measured CMC agreeing with the literature value of 2.25 mM.

The dynamics of polymer bridge formation and disruption and its effect on the bulk rheology of suspensions.

Bridge-flocculated colloidal gels are used in many important processes and products such as gel casting for advanced ceramics, precursor inks for 3D printing, and waste treatment strategies. An important aspect of polymer bridged gels that makes them excellent candidates for these applications is the precise control it affords for control of rheological properties. Recent studies have shown that adhesion between bridged surfaces increases with time as the number of polymer bridges formed grows. However, the consequences of the dynamics of these processes toward bulk rheological properties have not been studied. Here we investigate the link between the dynamics of polymer bridging and disruption and bulk rheology in dense colloidal silica particle suspensions flocculated by polyethylene oxide (PEO). Microscale pull-off force measurements using atomic force microscope (AFM) show that upon repeated disruption and establishment of bridged contact, the adhesion between the surfaces is reduced. During contact disruption, the polymer chains bridging the two surfaces are stretched leading to chain scission. On the re-establishment of contact, these fragmented polymer chains are unable to fully re-establish the adhesion. Macroscale measurements using oscillatory rheology show that this reduced adhesion results in reduction of both the storage modulus and the yield stress. If the slurry is subjected to high shear for long periods, polymer chain scission is amplified, and the fragmented polymer chains are unable to bridge the particles again, resulting in free-flowing slurries.

Investigation of surfactant mediated acid-base charging of mineral oxide particles dispersed in apolar systems.

The current work examines the role of acid-base properties on particle charging in apolar media. Manipulating the polarity and magnitude of charge in such systems is of growing interest to a number of applications. A major hurdle to the implementation of this technology is that the mechanism(s) of particle charging remain a subject of debate. The authors previously conducted a study of the charging of a series of mineral oxide particles dispersed in apolar systems that contained the surfactant AOT. It was observed that there was a correlation between the particle electrophoretic mobility and the acid-base nature of the particle, as characterized by aqueous point of zero charge (PZC) or the isoelectric point (IEP). The current study investigates whether or not a similar correlation is observed with other surfactants, namely, the acidic Span 80 and the basic OLOA 11000. This is accomplished by measuring the electrophoretic mobility of a series of mineral oxides that are dispersed in Isopar-L containing various concentrations of either Span 80 or OLOA 11000. The mineral oxides used have PZC values that cover a wide range of pH, providing a systematic study of how particle and surfactant acid-base properties impact particle charge. It was found that the magnitude and polarity of particle surface charge varied linearly with the particle PZC for both surfactants used. In addition, the point at which the polarity of charge reversed for the basic surfactant OLOA 11000 was shifted to a pH of approximately 8.5, compared to the previous result of about 5 for AOT. This proves that both surfactant and particle acid-base properties are important, and provides support for the theory of acid-base charging in apolar media.

Extension to the charge fluctuation model for the prediction of the conductivity of apolar, reverse micellar systems.

This paper presents an extension to current theory regarding charging behavior in apolar, micellar systems. Electrical conductivity in such systems accompanying the formation of neutral reverse micelles is commonly explained by the possibility of intermicellar collisions resulting in a pair of oppositely charged micelles. The sequestration of the resulting charges within the micelles prevents their immediate recombination. The current theory underlying the charging process has thus far been applied in only approximate form, and is only used to validate experimental trends and to abstract values for the fraction of charged micelles. The extended theory proposed here uses knowledge of the solvent and surfactant characteristics, together with water content, to predict solution conductivity in absolute terms. It is verified in experiments with the solvent Isopar-L and surfactants Aerosol OT, OLOA 11000, and Span 80, in which significant differences from the approximate theory are observed.

Characterization of mineral oxide charging in apolar media.

This paper presents an investigation of the charging behavior of mineral oxide particles dispersed in apolar media. There are a growing number of applications that seek to use electrostatic effects in apolar media to control particle movement and improve aggregation stability. Progress is limited, however, by incomplete knowledge of the mechanism(s) of particle charging in these systems. It has been shown in a number of cases that the acid-base properties of both the particles and the surfactants used to stabilize charge play key roles. A mechanism for acid-base charging has previously been established for mineral oxides in aqueous systems, where the surface hydroxyl groups act as proton donors or receivers depending on the pH of the surrounding solution. In water, the pH at which the surface charge density is zero, i.e., the point of zero charge (PZC), can be used to characterize the acid-base nature of the mineral oxide particles. The current work explores the possible extension of this charging behavior to apolar systems, with the key difference that the surface hydroxyl groups of the mineral oxides react with the surfactant molecules instead of free ions in solution. The apolar charging behavior is explored by measuring the electrophoretic mobility of a series of mineral oxides dispersed in a solution of Isopar-L and AOT, a neutral surfactant in water. The electrophoretic mobility of the particles is found to scale quantitatively, with respect to both sign and magnitude, with their aqueous PZC value. This provides support for the theory of acid-base charging in apolar media and represents a method for predicting and controlling particle charge of mineral oxides dispersed in apolar media.

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.

Electroacoustics of particles dispersed in polymer gel.

This study examines the electroacoustics of particles dispersed in polymer hydrogels, with the particle size either less than or greater than the gel mesh size. When the particles are smaller than the gel mesh size, their acoustic vibration is resisted by only the background water medium, and the measured dynamic electrophoretic mobility, µ(d) (obtained in terms of colloid vibration current, CVI), is the same as that in water. For the case of particles larger than the gel mesh size, µ(d) is decreased due to trapping, and the net decrease depends on the viscoelastic properties of the gel. The gel mesh size was varied by varying its cross-link density, with the latter being characterized as the storage modulus, G'. The dependence of mobility on G', for systems of a given particle size, and on particle size, for gels of a given G', are investigated. The measured mobility remains constant as G' is increased (i.e., mesh size is decreased) up to a value of approximately 300 Pa, beyond which it decreases. In the second set of measurements, the trapped particle size was increased in a gel medium of constant mesh size, with G' being approximately 100 Pa. In this case, the measured µ(d) is found to be effectively constant over the particle size range studied (14-120 nm); that is, it is independent of the degree of trapping as expressed by the ratio of the particle size to the mesh size.

Acoustic spectroscopy of colloids dispersed in a polymer gel system.

The technique of acoustic spectroscopy offers some significant advantages over conventional techniques, such as dynamic light scattering and differential sedimentation (centrifugation), for the characterization of colloidal dispersions in that it does not require that the systems be highly dilute and transparent. Another advantage of the method may derived from the fact that in applications, the relative motion between any particle and the medium is very small, at the most being comparable to the particle size. It may thus be suited, within limits, to the study of dispersions in polymer gels, without the additional limitation of conventional methods to transparent media (matching refractive index of polymer and liquid). The present work seeks to probe experimentally the limits of the technique and its current theory for the determination of particle size distributions in gel media. Experiments measuring acoustic attenuation have been conducted on dispersions of silica particles of varying size in aqueous hydroxylpropyl cellulose (HPC) gels of varying cross-link density. The particle size distribution (PSD) was successfully measured by acoustic attenuation theory for dispersions in Newtonian media provided that the hydrodynamic particle diameter was less than the hydrodynamic mesh size of the gel, as given by simple rubber elasticity theory (mesh size/particle size ≳1.5). The same results were obtained at particle loadings of up to 15 wt %. If the particles are larger than the mesh size, then a viscoelastic response from the gel matrix is observed that cannot be interpreted to yield the particle size using the existing theoretical framework.

The dynamic interaction of water with four dental impression materials during cure.

PURPOSE: The purpose of this work was to investigate the interaction of water with four different dental impression materials: Aquasil (Ultra XLV Type 3), Take 1 (Wash Regular Set), Genie (Light Body, Standard Set), and Impregum Garant (Soft Light Bodied Consistency). MATERIALS AND METHODS: Apparent contact angles of de-ionized water made against thin horizontal sample films of the different materials under different conditions were measured from analysis of profile images of symmetrical sessile drops of water placed on the sample films using a Model FTA200 dynamic drop shape analysis system, which included a JAI M30 high speed CCD camera combined with a zoom microscope. Data were taken for specimens of dry ages (times following mixing) from a minimum of 20 seconds up to 1220 seconds. Imaging was started before the initial water/impression material contact, and lasted for at least 420 seconds in each case. The interval at the beginning of each run was 0.033 second, and then increased by a factor of 1.012 to the end. During the initial 3 seconds following the drop deposition, the drop's shape oscillated due to inertial effects, so apparent contact angle data during this period were neglected in all cases. All measurements were made at room temperature. The drops were enclosed in a humidified chamber that suppressed evaporation. All data were repeated at least five times, and results were analyzed where appropriate using one-way ANOVA. Microscopic images of the water/impression material interactions for fresh (uncured) materials were acquired to reveal the destructive interactions that resulted from such contact. Finally, surface tension measurements were made of water that had been contacted with material of varying dry age using the pendant drop method capability of the drop shape analysis system. These helped to assess the origin of hydrophilicity development for the different materials. RESULTS: For short curing times (dry ages), water showed a destructive effect on the integrity of all of the impression materials, as evidenced by the formation of a crater beneath the water drop and a scum of material at its surface. These effects diminished with dry age until a critical curing time was reached, beyond which such destructive interactions were no longer detectable. These critical curing times were determined to be 80, 140, 110, and 185 seconds for Aquasil, Take 1, Genie, and Impregum, respectively. The initial contact angle following the respective critical curing time was lowest for Impregum, at 66 degrees ; while values for Aquasil, Genie, and Take 1 were 93 degrees , 104 degrees , and 110 degrees , respectively. Beyond the critical curing times for the different materials, different degrees of hydrophilicity were observed. Aquasil showed the lowest final contact angle (<10 degrees ), with Impregum, Take 1, and Genie showing 31 degrees , 34 degrees , and 40 degrees , respectively. Measurements of the surface tension of water after contact with the different materials suggested that for Aquasil, hydrophilicity appears to be developed through the leaching of surfactant from the material, whereas for Impregum, Take 1, and Genie, hydrophilicity is developed at least in part through a change in surface structure in contact with water. Impregum and Aquasil materials of dry ages well beyond the critical curing time exhibited a stick-slip behavior in their interline movement or contact angle evolution. This was believed to be due to the slowness in the leaching of surfactant (in the case of Aquasil) or the re-orientation of unleachable surface groups (in the case of the other materials) in comparison to the inherent kinetics of water drop spreading. CONCLUSIONS: All materials investigated in the fresh, uncured state showed qualitative decomposition when put in contact with water through the formation of a crater beneath the water drop and a scum of material at its surface. These effects diminished with curing time until beyond a critical value, no such effects were evident. The initial hydrophilicity of the materials as determined by the contact angles obtained at their respective critical dry ages was greatest for Impregum. Beyond the critical curing time, different degrees of hydrophilicity were observed, with Aquasil showing the lowest final contact angle.

Spreading on and penetration into thin, permeable print media: application to ink-jet printing.

This paper examines spreading and penetration of surfactant-laden drops on thin-permeable media with reference to ink-jet printing. A detailed review of the interaction of both pure liquids and surfactant containing solutions with porous substrates is given for individual spreading and penetration and for the combined processes. A new model based on energy arguments is derived and compared to current hydrodynamic equations used to describe simultaneous spreading and penetration. Three studies of how surfactant solutions interact with thin commercial ink-jet photographic quality papers are presented. Here, two relevant systems are examined: Tergitol 15-S-5 and 1,2-octanediol. The first study examines the spreading and penetration profiles for surfactant solutions over a range of concentrations spanning their critical micelle concentration. As expected, these profiles depend on the concentration of surfactant and the chemistry of the medium with which it interacts. In many cases, partial vertical penetration of the region directly beneath the drop dominates at low interaction times and will be significant in ink-jet applications. The second study consists of a parametric investigation of the energy-based model derived herein. It shows that the model can capture all of the behaviors observed in the first study. In the final study, the ability of the energy-based model to fully predict the spreading behavior of Tergitol 15-S-5 solutions is tested. It is found that the model produces good quantitative agreement at the highest concentrations and, as such, will be useful in screening spreading dynamics concentrated systems like ink-jet inks. Agreement at low to intermediate concentrations is often limited by finite induction periods prior to significant spreading and penetration. Possible corrections that could improve the agreement for weakly concentrated solutions are discussed, and directions for future studies of simultaneous spreading and penetration are proposed.

High-salt stabilization of Laponite clay particles.

Colloidal radioactive transuranic wastes are currently buried in large tanks in the form of dense colloids in high salt, high pH aqueous media. These facilities are beginning to fail, so it is necessary to transport and "package" them for more permanent disposal, processes requiring understanding of the microstructure that develops under such conditions. Laponite RD clay is believed to be a good simulant for the colloids in the waste tanks, and the present study addresses their behavior under high salt conditions, where previous studies have frequently observed the phenomenon of "restabilization," i.e., the attainment of aggregation stability at high electrolyte conditions. Specifically, the aggregation kinetics and the resulting cluster structure (fractal dimension) of Laponite RD clay colloids at high concentrations of BaCl2 (an electrolyte previously shown to lead to restabilization) are investigated. At low-to-intermediate electrolyte concentrations, the clay is found to behave in accord with DLVO theory, i.e., low salt conditions yield slow aggregation into densely-packed aggregates, whereas intermediate salt concentrations, sufficient to cause double layer collapse, produce rapid aggregation into open aggregates. High salt concentrations, however, show slow rates of aggregation. The aggregate structure under these conditions is found to mimic that found for very low electrolyte concentrations, i.e., high fractal dimension. Further experiments show that a sudden increase in salt concentration in a system containing young open aggregates produced under intermediate salt concentrations causes them to reform into more compact structures.

Relating clay yield stress to colloidal parameters.

The ability to predict rheological behavior of clay dispersions would be useful in formulating systems rheologically modified by clays as well as designing equipment to handle clay based materials. Deriving predictive equations for these materials has been hindered due to the various mechanisms by which clay systems develop microstructure. This work seeks to observe the relationship between the yield stress, tauy, and the zeta potential, zeta, and determine the nature of the particle interactions for dispersions of laponite (a synthetic clay) and dispersions of a mixture of naturally occurring kaolinites and bentonites. It is found that the relationship of tauy to zeta2 for clay suspensions is opposite to that found for homogeneously charged spheroidal colloids. This result can be traced to the type of particle interactions occurring, which for the systems studied appear to be edge-to-face attractions.

Gel trapping of dense colloids.

Phase density differences in sols, foams, or emulsions often lead to sedimentation or creaming, causing problems for materials where spatial uniformity over extended periods of time is essential. The problem may be addressed through the use of rheology modifiers in the continuous phase. Weak polymer gels have found use for this purpose in the food industry where they appear to be capable of trapping dispersoid particles in a three-dimensional matrix while displaying water-like viscosities at low shear. Attempts to predict sedimentation stability in terms of particle properties (size, shape, density difference) and gel yield stress have led to qualitative success for suspensions of large particles. The effect of particle size, however, in particular the case in which colloidal dimensions are approached, has not been investigated. The present work seeks to determine useful stability criteria for colloidal dispersions in terms of readily accessible viscoelastic descriptors. Results are reported for systems consisting of 12 microm poly(methyl methacrylate) (PMMA) spheres dispersed in aqueous gellan gum. Monovalent salt concentration is varied to control rheological properties, and sedimentation/centrifugation experiments are performed to determine dispersion stability. Necessary conditions for stability consist of a minimum yield stress together with a value of tan delta less than unity.

The role of acid-base effects on particle charging in apolar media.

The creation and stabilization of electric charge in apolar environments (dielectric constant≈2) have been an area of interest dating back to when an explanation was sought for the occurrence of what are now known as electrokinetic explosions during the pumping of fuels. More recently attention has focused on the charging of suspended particles in such media, underlying such applications as electrophoretic displays (e.g., the Amazon Kindle® reader) and new printing devices (e.g., the HP Indigo® Digital Press). The endeavor has been challenging owing to the complexity of the systems involved and the large number of factors that appear to be important. A number of different, and sometimes conflicting, theories for particle surface charging have been advanced, but most observations obtained in the authors' laboratory, as well as others, appear to be explainable in terms of an acid-base mechanism. Adducts formed between chemical functional groups on the particle surface and monomers of reverse micelle-forming surfactants dissociate, leaving charged groups on the surface, while the counter-charges formed are sequestered in the reverse micelles. For a series of mineral oxides in a given medium with a given surfactant, surface charging (as quantified by the maximum electrophoretic mobility or zeta potential obtained as surfactant concentration is varied) was found to scale linearly with the aqueous PZC (or IEP) values of the oxides. Different surfactants, with the same oxide series, yielded similar behavior, but with different PZC crossover points between negative and positive particle charging, and different slopes of charge vs. PZC. Thus the oxide series could be used as a yardstick to characterize the acid-base properties of the surfactants. This has led directly to the study of other materials, including surface-modified oxides, carbon blacks, pigments (charge transfer complexes), and polymer latices. This review focuses on the acid-base mechanism of particle charging in the context of the many other factors that are important to the phenomenon, including the presence of water, of other components (e.g., synergists and contaminants), and of electric field effects. The goal is the construction of a road map describing the anticipated particle charging behavior in a wide variety of systems, assisting in the choice or development of materials for specific applications.

Effect of surfactant hydrophile-lipophile balance (HLB) value on mineral oxide charging in apolar media.

The current work examines the role of surfactant hydrophile-lipophile balance (HLB) on the ability for surfactant reverse micelles to impart charge to particles dispersed in an apolar medium, a study motivated by a number of applications that seek to maximize particle charge in such systems. Previous investigations have shown that relative acid-base properties of the particles and surfactants, as well as surfactant concentration and trace water content, all play a major role in the particle charge obtained. However, the ability of a surfactant to stabilize charge in reverse micelles is also an important aspect of creating charge on a particle surface. It has been previously shown that surfactant HLB value is an important parameter in assessing the size of the polar core of the reverse micelles, thereby impacting the total charge that is generated in the bulk solution as determined by conductivity. In the current study, this theory is extended to investigate the impact on particle charging. To accomplish this, the electrophoretic mobility is determined for a series of mineral oxides dispersed in Isopar-L with either Span 20, Span 80, or Span 85. These three surfactants all have the same head group chemistry, but their HLB value ranges from 1.8 to 8.6. It is found that the maximum observed particle electrophoretic mobility does scale directly with the HLB of the accompanying surfactant. This indicates that there is a direct correlation between a surfactant's ability to stabilize charge and its ability to impart charge to a particle. However, the largest HLB surfactant, Span 20, also exhibited a large amount of charge screening or neutralization at larger surfactant concentrations. This highlights the competition between particle charging and micelle-micelle charging that remains one of the largest obstacles to maximizing particle charge in apolar systems.

A review of the different techniques for solid surface acid-base characterization.

In this work, various techniques for solid surface acid-base (AB) characterization are reviewed. Different techniques employ different scales to rank acid-base properties. Based on the results from literature and the authors' own investigations for mineral oxides, these scales are compared. The comparison shows that Isoelectric Point (IEP), the most commonly used AB scale, is not a description of the absolute basicity or acidity of a surface, but a description of their relative strength. That is, a high IEP surface shows more basic functionality comparing with its acidic functionality, whereas a low IEP surface shows less basic functionality comparing with its acidic functionality. The choice of technique and scale for AB characterization depends on the specific application. For the cases in which the overall AB property is of interest, IEP (by electrokinetic titration) and H(0,max) (by indicator dye adsorption) are appropriate. For the cases in which the absolute AB property is of interest such as in the study of adhesion, it is more pertinent to use chemical shift (by XPS) and the heat of adsorption of probe gases (by calorimetry or IGC).