Zeta potential experimental measurements

The numerical optimization methods do not require additional assumptions of the temporal constancy, or even neglect some physical constants, for example surface potential. Used for the optimization of the edl parameters (surface hydroxyl group reaction constants, capacity and density of adsorption sites) the numerical methods allow us to find the closest values to the experimentally available data (surface charge density, adsorption of ions, zeta potential, colorimetric measurements). Usually one aims to find the parameters, accepted from physical point of view, where a function, that expresses square of the deviation between calculated and measured values will be the smallest. 

The equations do not take into account the finite size of the ions the potential to be used is ipi, the potential at the Stern plane (the plane of closest approach of ions to the surface), which is difficult to measure. The nearest experimental approximation to is often the zeta potential (0 measured by electrophoresis. 

Additional to the sedimentation behaviour, the zeta-potential was measured for each suspension. This was conducted by means of an electroacoustic measurement technique (Sect. 2.3.7.2). The technique yields an effective zeta-potential of the binary suspension, which is calculated from the electroacoustic raw signals by assuming effective particle properties (e.g. for the permittivity and density of the solid material). When the two particle components contribute independently to the electroacoustic signal and do not affect each other with regard to the interfacial properties, it is possible to calculate the effective zeta-potential from the zeta-potentials of the single components. The comparison between such calculated zeta-potential values with experimental ones allows a first evaluation of the interfacial phenomena in the binary suspension. 

One can write acid-base equilibrium constants for the species in the inner compact layer and ion pair association constants for the outer compact layer. In these constants, the concentration or activity of an ion is related to that in the bulk by a term e p(-erp/kT), where yp is the potential appropriate to the layer [25]. The charge density in both layers is given by the algebraic sum of the ions present per unit area, which is related to the number of ions removed from solution by, for example, a pH titration. If the capacity of the layers can be estimated, one has a relationship between the charge density and potential and thence to the experimentally measurable zeta potential [26]. 

An important reason for this lack of experimental work is that the zeta-potential cannot be easily determined independent of the electrophoretic mobility [284] however, in the case of proteins (as well as some other charged colloids), the intrinsic charge obtained by titration is a parameter that can be measured independent of the electrophoretic mobility. The charge obtained from electrophoretic measurements (i.e., the net charge) via the preceding theories is generally not the same as the charge obtained from titration (i.e., the in-... 

The surface potential is not accessible by direct experimental measurement it can be calculated from the experimentally determined surface charge (Eqs. 3.1 - 3.3) by Eqs. (3.3a) and (3.3b). The zeta potential, calculated from electrophoretic measurements is typically lower than the surface potential, y, calculated from diffuse double layer theory. The zeta potential reflects the potential difference between the plane of shear and the bulk phase. The distance between the surface and the shear plane cannot be defined rigorously. 

There is no experimental way to measure y. (As we mentioned before, the zeta potential - as obtained, for example, from electrophoretic measurments - is in a not readily definable way - smaller than y.) But as discussed in section 3.3 we can obtain the surface charge (Eq. 3.2) and then compute the surface potential y on the basis of the diffuse double layer model with Eq. (3.8a) Eq. (3.8a) in simplified form for 25° C is... 

One possible solution is to obtain new experimental data, which is independent of co/pH curves. The zeta potential is of course a possibility, but it suffers from the intrinsic indeterminacy of the exact location in the double layer where it occurs. Another possibility is the surface potential, Vo, which will be defined below. Variations of Vo can be measured by using electrolyte/insulator/semiconductor structures. It has been shown by Bousse et al. (14) that the Vo/pH characteristics are determined mainly by the number of charged but uncomplexed surface sites, and are insensitive to complex-ation. This means that combined consideration of tro/pH and Vo/pH characteristics should lead to a more complete and reliable determination of model parameters. 

Table 7.2 Effect of the presence of an anionic polysaccharide on the measured zeta potential (Q of emulsion droplets stabilized by proteins under experimental conditions corresponding to protein-polysaccharide complexation. In all cases the complexes were formed in the bulk aqueous medium before emulsification.

The Nemst equation applies (if we neglect the activity coefficients of the ions, in keeping with PB theory) to the emf (electromotive force) of an electrochemical cell. The emf of such a cell and the surface potential of a colloidal particle are quantities of quite different kinds. It is not possible to measure colloidal particle with a potentiometer (where would we place the electrodes ), and even if we could, we have no reason to expect that it would obey the Nemst equation. We have been at pains to point out that all the experimental evidence on the n-butylam-monium vermiculite system is consistent with the surface potential being roughly constant over two decades of salt concentration. This is clearly incompatible with the Nemst equation, and so are results on the smectite clays [28], Furthermore, if the zeta potential can be related to the electrical potential difference deviations from Nemst behavior, as discussed by Hunter... 

The work of Larson et al. (62) represented the first detailed study to show agreement between AFM-derived diffuse layer potentials and ((-potentials obtained from traditional electrokinetic techniques. The AFM experimental data was satisfactorily fitted to the theory of McCormack et al. (46). The fitting parameters used, silica and alumina zeta-potentials, were independently determined for the same surfaces used in the AFM study using electrophoretic and streaming-potential measurements, respectively. This same system was later used by another research group (63). Hartley and coworkers 63 also compared dissimilar surface interactions with electrokinetic measurements, namely between a silica probe interacting with a polylysine coated mica flat (see Section III.B.). It is also possible to conduct measurements between a colloid probe and a metal or semiconductor surface whose electrochemical properties are controlled by the experimenter 164-66). In Ref. 64 Raiteri et al. studied the interactions between... 

We shall describe a simple and low-cost method of tracking particles in three dimensions that is efficient for a particle diameter of about 0.5 pm to 1 mm. After a section devoted to the experimental device we shall give different examples of utilization size and density determination, measurement of zeta potential, measurement of roughness. In the last section we shall discuss some other methods and compare their respective advantages. 

The frictional and adhesion forces between the abrasive particles and wafer surfaces were experimentally measured using alumina and silica slurries with and without citric acid. Although citric acid did not affect the zeta potential of the silica particles, it resulted in a more negative zeta potential of the alumina particles due to the adsorption of the negatively charged citrate ions onto the alumina surfaces. The highest particle adhesion force was measured in an alumina slurry without the addition of citric acid. However, the alumina slurry with the addition of citric acid had the lowest particle adhesion force due to the adsorption of citrate ions onto the alumina surfaces. Although citrate ions could easily adsorb onto alumina particles, the silica particles did not appear to benefit in terms of reduced frictional force when in citric acid solutions. 

The purpose of this study was to explore the interaction between slurry particles and wafer surfaces by the measurements of their zeta potentials. The zeta potentials of slurry particles such as fumed and colloidal silica, alumina, ceria and MnOj and substrates such as silicon, TEGS, W, and A1 have been measured by electrophoretic and electroosmosis method to evaluate the electrical properties of surfaces, respectively. The zeta potential of oxide and metal surfaces showed similar values to those of particles as a function of pH. The interaction energy between alumina and silica particles and TEOS, W and A1 substrate were calculated based on DLVO theory. No deposition of silica particles on TEOS and the heavy deposition of alumina particles on metal substrates were observed in the particle deposition test. Experimental results were well agreed with the theoretical calculation. 

Zeta potentials of slun particles and wafer surfaces were measured to calculate the DLVO total interaction energy between them at various pHs. Instead of the Debye-Huckel low potential approximation, Overbeek s approximate was applied to the calculation. The repulsive energy was calculated between silica and TEOS wafers. Particle dip test also showed no deposition of particles on TEOS wafer. Due to the low cell constant of conductive W plate, it was not possible to measure the zeta potentials of W. The Hamaker constants of A1 and W were calculated and applied to the calculation of total interaction energy. The theoretical calculation was agreed well with the experimental results. The strong attractive interaction between metal surfaces and alumina particles were observed in both the calculation and experiments. 

Determination of the Electrophoretic Mobility, To evaluate the equation for the double-layer interaction (eq 5), the zeta potential, must be known it is calculated from the experimentally measured electrophoretic mobility. For emulsions, the most common technique used is particle electrophoresis, which is shown schematically in Figure 4. In this technique the emulsion droplet is subjected to an electric field. If the droplet possesses interfacial charge, it will migrate with a velocity that is proportional to the magnitude of that charge. The velocity divided by the strength of the electric field is known as the electrophoretic mobility. Mobilities are generally determined as a function of electrolyte concentration or as a function of solution pH. 

Adsorption isotherms are habitually obtained using the solution depletion method, which consists of comparing the solute concentrations before and after the attainment of adsorption equilibrium. Electrokinetic or zeta potentials are determined by two techniques microelectrophoresis [12,14,17] and streaming potential [13,58,59]. The former is employed to measure the mobility of small particles of chemically pure adsorbents, whereas the latter is adopted to investigate the electrophoretic behaviour of less pure coarser mineral particles. A correlation between the adsorption and electrophoretic results is usually examined with the aim of sheding light on the mechanism by means of which the surfactants are adsorbed at the solution-solid interface. This implies the necessity of maintaining the same experimental conditions in both experiments. For this purpose, the same initial operational procedure is applied. 

However, the electrophoretic mobility calculated using Eq. (4) is usually not accurate and, in general, the electrophoretic mobility must be measured experimentally. An alternate expression for u, in terms of the zeta potential is given by Henry... 

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