Electrolyte-dependent multiparticle motion near electrodes in oscillating electric fields.

The directed assembly of micrometer-scale particles into hexagonal lattices on electrodes was probed by subjecting them to electric fields oscillating at 100 Hz. Solutions of KOH, NaHCO(3), and KCl were used because previous investigations of particle pair behavior had shown that an electrolyte-dependent phase angle dictates whether two particles aggregate or separate at low frequencies. Here it was found that particle ensembles, aggregating or separating, adopt a 2D hexagonal lattice in both cases; the difference appears in the particle spacing. For electrolytes such as NaHCO(3) and KCl, where two isolated particles aggregate, the gap between particle edges is between 1 and 1.5 particle diameters; in KOH, where two particles tend to separate, the interparticle spacing is several diameters.

Electrolyte-dependent pairwise particle motion near electrodes at frequencies below 1 kHz.

A model incorporating a phase angle between an applied electric field and the motion of particles driven by it explains electrolyte-dependent pairwise particle motion near electrodes. The model, predicting that two particles aggregate when this phase angle is greater than 90 degrees but separate when the phase angle is less than 90 degrees , was based largely on contrasting behavior in two electrolytes (KOH and NaHCO3) used with indium tin oxide (ITO) electrodes. The present contribution expands the experimental evidence for this model to KOH, NaHCO3, NaOH, NH4OH, KCl, and H2CO3 solutions with Pt, as well as ITO electrodes. The phase angle correlation was verified in all cases. Comparisons of the model predictions to experimental data show that the sign and order of magnitude of rates of change in the separation distances between particle pairs are correctly predicted.

Calculation of the streaming potential near a rotating disk.

A corrected theory of the streaming potential in the vicinity of a disk-shaped sample rotating in an electrolytic solution is presented. When streaming-potential measurements on a variety of materials were reduced to a zeta potential according to a prior theory, the results exceeded expected values by a factor of approximately 2, even though other aspects of the same experiments seemed to confirm the theory. Investigation of the source of the discrepancy revealed a flaw in the prior theory. The crucial understanding is that the surface current produced by the rotation of the disk emerges from the diffuse layer and enters the bulk solution at the periphery of the disk. The new treatment accounts entirely for the discrepancy between literature data and results based on the prior theory.

Measurement of the streaming potential and streaming current near a rotating disk to determine its zeta potential.

Methodology for determining the zeta potential of a disk-shaped sample by both streaming potential and streaming current measurements is presented. Integration of Laplace's equation within one radius of the disk surface revealed that the streaming potential decreased strongly in the surface normal direction. With this solution, the zeta potential can be calculated from measurements of the streaming potential near the surface of the disk provided the position of the working electrode near the disk surface is known. Determining the zeta potential of a disk-shaped sample by means of streaming current measurements required determination of a current collection efficiency because not all the streaming current from a disk flows through the auxiliary electronic current path. While the working electrode near the disk should be pointlike, several possible variants on counter electrode shape and size were explored. Although the current collection efficiency was only a few percent in each case, the measured current was of 10 nA order. The current collection efficiency depended only on system geometry and was independent of a disk's zeta potential and solution concentration. Streaming current measurements of zeta potential on silicon wafers in potassium chloride solutions up to 10 mM agreed well with published values.

Measurement of the zeta potential of planar solid surfaces by means of a rotating disk.

A method for measuring the zeta potential of disks is described. Combining the hydrodynamic properties of a rotating disk, the solution of Laplace's equation for the potential, and the electrokinetic boundary condition, one obtains an equation that relates the zeta potential of the disk to the streaming potential in the disk's vicinity. Theory predicts a dependence of the streaming potential on the rotation rate raised to the 3/2 power. Theory also shows that placement of one reference electrode on the axis of rotation near the disk surface and the other far from the disk is favorable. Measurement of the streaming potential of silicon oxide and indium tin oxide in contact with a solution of potassium chloride demonstrated the expected 3/2 power dependence on rotation rate. The zeta potentials calculated from the combination of the theory and experimental data agreed with published values.