Zeta potential colloid stability

Problem 10.4 Zeta potential and stability of colloids The following data are available from a measurement of the zeta potential in an aqueous polystyrene colloidal dispersion at 25 °C ... 

Many investigators of steric stabilization have measured colloidal stability without taking the effort to find out whether the stability actually resulted from electrostatic stabilization. In many published articles it has been concluded that steric stabilization had been attained and further study showed this was not the case. One such example is a recent paper on "steric" stabilization by an additive of the same type used in this work. (12) The published photograph shows the silica particles in oil stabilized at interparticle separations several times the distances provided by the adsorbed films no electrical measurements had been made, but it they had, this particular dispersant would have provided about -200 mV of zeta-potential and given excellent electrostatic repulsion. The reader should be wary of any claims of steric stabilization unless the electrostatic contribution has been measured. 

In such systems the requirement of the electrostatic contribution to colloidal stability is quite different than when no steric barrier is present. In the latter case an energy barrier of about 30 kT is desirable, with a Debye length 1/k of not more than 1000 X. This is attainable in non-aqueous systems (5), but not by most dispersants. However when the steric barrier is present, the only requirement for the electrostatic repulsion is to eliminate the secondary minimum and this is easily achieved with zeta-potentials far below those required to operate entirely by the electrostatic mechanism. 

The zeta potential of the formulations was determined by Doppler velocimetry and PCS on a Zetasizer 4 (Malvern Instruments, U.K.), without further dilution. The zeta potential of LC-AmB under these conditions was —44 mV, slightly lower than that measured for the same lipid composition without AmB, —55 mV, but remaining consistent with colloidal stability. This reduction in the absolute value of the zeta potential could be due to the presence of AmB at the surface, because free AmB dispersed in water under the same conditions had a less negative zeta potential about —27 mV. 

In another application, the magnitude of the zeta potential is measured as a function of added counterions. The variation in zeta potential is found to be related to the stability of the colloidal suspension. The results of a gold colloidal suspension (gold solute) are reported as follows ... 

The well-known DLVO theory of colloid stability (10) attributes the state of flocculation to the balance between the van der Waals attractive forces and the repulsive electric double-layer forces at the liquid—solid interface. The potential at the double layer, called the zeta potential, is measured indirectly by electrophoretic mobility or streaming potential. The bridging flocculation by which polymer molecules are adsorbed on more than one particle results from charge effects, van der Waals forces, or hydrogen bonding (see COLLOIDS). 

Since the micelles are closely packed, intermicellar collisions are frequent however, the micelles do not normally remain together after collisions. The micelles are stabilized by two principal factors (1) a surface (zeta) potential of c. —20 mV at pH 6.7, which, alone, is probably too small for colloidal stability, and (2) steric stabilization due to the protruding K-casein hairs. 

Throughout most of this chapter the emphasis has been on the evaluation of zeta potentials from electrokinetic measurements. This emphasis is entirely fitting in view of the important role played by the potential in the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability. From a theoretical point of view, a fairly complete picture of the stability of dilute dispersions can be built up from a knowledge of potential, electrolyte content, Hamaker constants, and particle geometry, as we discuss in Chapter 13. From this perspective the fundamental importance of the f potential is evident. Below we present a brief list of some of the applications of electrokinetic measurements. 

ZETA POTENTIAL. The potential across the interface of all solids and liquids. Specifically, the potential across the diffuse layer of ions surrounding a charged colloidal particle, which is largely responsible for colloidal stability. Discharge of the zeta potential, accompanied by precipitation of the colloid, occurs by addition of polyvalent ions of sign opposite to that of the colloidal particles. Zeta potentials can be calculated from electrophoretic mobilities, i.e., the rates at which colloidal particles travel between charged electrodes placed in the solution. 

Figure 5.9 Illustration of the effect of electrolyte on colloid stability. The photomicrographs A through D show how 1.1 tm size silica particles are progressively coagulated by increasing additions of alum (0, 10, 30, 40 ppm, respectively). The corresponding zeta potentials are -30 mV (A), -14 mV (B), -6 mV (C), and -0 mV (D). From Zeta-Meter [544], Courtesy L.A. Ravina, Zeta-Meter, Inc., Staunton, Va.

One can attribute the relative stability of colloids, or dispersed particles, to a theoretical electrokinetic potential, or zeta potential, or potential, which is defined as the potential difference between the bulk solvent and a very thin layer of the solvent (called the "slipping plane" and typically about lnm thick) that is tightly attached to the colloidal particle or nanoparticle. This potential cannot be measured directly, but... 

Temperature- and pH-sensitive core-shell microgels consisting of a PNIPAAm core crosslinked with BIS and a polyvinylamine (PVAm) shell were synthesized by graft copolymerization in the absence of surfactant and stabilizer [106] The core-shell morphology of the microgels was confirmed by TEM and zeta-potential measurements. Other examples of core-shell microgel systems are PNIPAAm-g-P(NIPAM-co-styrene) colloids [107] or PS(core)-g-PNIPAAm (shell) particles [108],... 

The W values [65] for a dispersion of AI2O3 as a function of pH and KNO3 salt concentration are shown in Figure 10.27. The AI2O3 particles are colloidally stable far away from their isoelectric point (i.e., pH 8.9). As the salt concentration is increased the zeta potential decreases and the colloid stability ratio, W, decreases. Near the isoelectric point there is no electrostatic repulsion, giving a rapid coagulation. 

FIGURE 10.27 (a) Zeta potential as a function of pH for A1203 in an indifferent 1 1 electrolyte solution (i.e., l Os). (b) Colloid stability ratio for the same AI2O3 sol as a function of pH. The minimum values correspond to the isoelectric point at pH == 9. Data from Wiese and Healy [65]. 

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