Assembly of colloidal particles into microwires using an alternating electric field

We have investigated the dielectrophoretic assembly of colloidal gold, carbon black, and carbon nanotubes into electrical wires. The resulting microwires have diameters less than 1 microm, with lengths ranging from 5 microm to 3 mm. Current-voltage curves for these wires indicate an ohmic response, where the resistance is determined by the type of colloid and by the frequency of the alternating field used to grow the wires. The predicted frequency dependence of dielectrophoresis is confirmed by experiment. Measurements of the threshold voltage for initial wire growth are also presented. These experiments demonstrate that a variety of nanoparticles can be assembled into microwires for sensor applications.     

Movement of colloidal particles in two-dimensional electric fields

We characterize the movement of carbon black particles in inhomogeneous, two-dimensional dc electric fields. Motivated by display applications, the particles are suspended in a nonpolar solvent doped with a charge control agent. The two-dimensional fields are generated between strip electrodes on a glass slide spaced 120 microm apart with field strengths up to 10(4) V/m. Such fields are insufficient to drive either electrohydrodynamic instabilities or natural convection due to ohmic heating, but they move the particles between the electrodes in about 30 s. In the center region between the strip electrodes, the particles move by electrophoresis; that is, the particle velocity is proportional to the electric field. However, when imposing a constant-potential or constant-current boundary condition at the electrodes to derive the electrical field, the electrophoretic mobility calculated from the measured particle velocities is outside the range of mobilities predicted from the theory of O'Brien and White. Near the electrodes the particles either speed up or slow down, depending on the polarity of the electrode, and these changes in velocity cannot be explained simply by electrophoresis in a spatially varying electric field. We suggest that this anomalous motion arises from electrohydrodynamic flows originating from the interaction between the space charge of the polarized layers above the electrodes and the electric field. Approximate calculations indicate such flows could be sufficiently strong to explain the anomalous trajectories near the edges of the electrodes.     

Polarization and interactions of colloidal particles in ac electric fields

Micrometer-sized polystyrene particles form two-dimensional crystals in alternating current (ac) electric fields. The induced dipole-dipole interaction is the dominant force that drives this assembly. We report measurements of forces between colloidal particles in ac electric fields using optical tweezers and find good agreement with the point dipole model. The magnitude of the pair interaction forces depends strongly on the bulk solution conductivity and decreases as the ionic strength increases. The forces also decrease with increasing field frequency. The salt and frequency dependences are consistent with double layer polarization with a characteristic relaxation frequency omega(CD) approximately a(2)/D, where a is the particle radius and D is the ion diffusivity. This enables us to reinterpret the order-disorder transition reported for micrometer-sized polystyrene particles [Lumsdon et al., Langmuir 20, 2108 (2004)], including the dependence on particle size, frequency, and ionic strength. These results provide a rational framework for identifying assembly conditions of colloidal particles in ac fields over a wide range of parameters.     

Dynamic templating of colloidal patterns in three dimensions with nonuniform electric fields

Order-disorder transitions in colloidal systems are an attractive option for making switchable materials. Electric-field-driven order-disorder transitions are especially attractive for this purpose because the tuning parameter is easily and externally controllable. However, precise positional control of 3D structure is immensely challenging. Using patterned electrodes, we demonstrate that ac electric fields-dominantly dielectrophoresis (DEP) coupled with an electrohydrodynamic mechanism consisting of induced-charge electro-osmosis (ICEO)-can be used to template colloidal order dynamically in three dimensions. We find that the electric field geometry dictates the location, size, and shape of colloidal patterns and can produce patterns with surprising complexity.     

One-, two-, and three-dimensional superstructures of gold nanorods induced by dimercaptosuccinic acid

A method is described for assembling gold nanorods into one-, two-, and three-dimensional superstructures. The addition of dimercaptosuccinic acid (DMSA) into the nanorod solution was found to induce self-assembly of the latter to one-dimensional "tapelike", two-dimensional "sheetlike" and three-dimensional "superlattice-like" structures depending on the DMSA concentration. The assembly was found to follow a smectic structure, where the nanorod long axes are parallel to each other. The rods are spaced 8.5 +/- 0.3 nm apart in the resulting structures, which extend over several micrometers in length. Organizations perpendicular to the grid were also found. The nanorod tapes were found to bend, and they form circular assemblies as well. The assembly and morphology of the nanorod structures were characterized by transmission electron microscopy and UV-vis spectroscopy. The effect of the DMSA concentration as well as the pH of the medium was also studied. On the basis of several control experiments utilizing similar molecules, charge neutralization of the nanorods by the carboxylic group of DMSA was found to be the principal reason for such an assembly, while the mercapto groups render additional stability to its structure. A mechanistic model of the assembly is proposed. This type of assembly would plausibly function as a plasmonic waveguide in potential nanodevices.     

In situ conductance measurements for alignments of silica particles under alternating electric fields

The alignments of silica particles formed in sinusoidal electrical fields of 1 kHz were assessed using an optical microscope with measuring the electric conductance of a silica dispersion between two Pt electrodes in a vitreous silica glass cell. We confirmed that the electric conductance of the silica dispersion between the two electrodes in the cell reflected the surface conductance of the silica particles settling at the bottom of the cell. More interestingly, we observed that the electric conductance of the silica dispersion in the cell increased when pearl chains of the silica particle were formed along the direction of the electric field. However, no clear change in the electric conductance of the dispersion was observed at higher electric field strengths where a transition from pearl chains to zigzag band patterns and circulating movements of the silica particles in the zigzag bands formed.     

Nonlinear current in modified nanotubes with exposure to alternating and constant electric fields

Nonlinear current density was studied as a function of the value of alternating and constant electric fields in modified carbon nanotubes (CNTs). The nonlinear current value in modified CNTs is one to two orders of magnitude higher than in unmodified CNTs. This trend makes it possible to decrease the surface density in an ensemble of weakly interacting nanotubes in considering the problem of electromagnetic radiation generation.     

Differences in the electrorheological response of a particle suspension under direct current and alternating current electric fields

We have observed an unusual reduction of shear stress with increasing shear rate under direct current electric fields, for an electrorheological fluid composed of sulfonated poly(styrene-co-divinylbenzene) particles dispersed in silicone oil. At all shear rates, the shear stress under the electric field is larger than that in the absence of the field, indicating that there is still some field-induced agglomeration of the particles. In contrast, the behavior under alternating current electric fields is the Bingham-fluid-type response commonly observed with electrorheological fluids. It is suggested that the conventional dipole–dipole interaction approach based on simplified microstructural models would be unable to explain these phenomena. Received: 27 November 2000 Accepted: 22 May 2001     

Concentrating particles on drop surfaces using external electric fields

We propose to use an externally applied uniform electric field to alter the distribution of particles on the surface of a drop immersed in another immiscible liquid. Specifically, we seek to generate well-defined concentrated regions at the drop surface while leaving the rest of the surface particle free. Experiments show that when the dielectric constant of the drop is greater than that of the ambient liquid the particles for which the Clausius-Mossotti factor is positive move along the drop surface to the two poles of the drop. Particles with a negative Clausius-Mossotti factor, on the other hand, move along the drop surface to form a ring near the drop equator. The opposite takes place when the dielectric constant of the drop is smaller than that of the ambient liquid, namely particles for which the Clausius-Mossotti factor is positive form a ring near the equator while those for which such a factor is negative move to the poles. This motion is due to the dielectrophoretic force that acts upon particles because the electric field on the surface of the drop is nonuniform, despite the uniformity of the applied electric field. Experiments also show that when small particles collect at the poles of a deformed drop the electric field needed to break the drop is smaller than without particles. These phenomena could be useful to concentrate particles at a drop surface within well-defined regions (poles and equator), separate two types of particles at the surface of a drop or increase the drop deformation to accelerate drop breakup.     

Experimental study of the effect of external electric fields on interfacial dynamics of colloidal particles

The interaction of colloidal particles with a planar surface (i.e., wall) in the presence of an electric field applied parallel to the planar surface is of interest in various microfluidic devices. Evanescent wave-based particle-tracking velocimetry was used to investigate the dynamics of a dilute suspension of polystyrene and silica particles (radii a = 110-463 nm) in a monovalent electrolyte solution with a Debye length of 6.8 nm driven through a microchannel by external electric fields E = 15-31 V/cm over the first 300 nm next to the channel wall. The particle velocity parallel to the wall due to electrophoresis and electroosmosis was in good agreement with the Helmholtz-Smoluchowski relation, and the hydrodynamic interactions between the wall and the particles were negligible, for all particle types. Measurements of the distribution of particles along the wall-normal coordinate, however, suggest that an additional force as great as 30 fN that repels the negatively charged particles away from the wall is induced by nonzero E. The results suggest that the magnitude of this force scales as E(2) and a(2) but is independent of the particle ζ-potential, in agreement with previous theoretical studies. However, estimates of the force assuming that the particles have a Boltzmann distribution were up to 40 times greater than the theoretical predictions, which only considered "remote" particle-wall interactions. These results are, to our knowledge, the first to observe a repulsive wall-normal force due to an applied electric field for near-wall colloidal particles.     

Appearance of nonuniform electric fields in solid ionic conductors

A computer model is used to study charge transport in ionic materials upon the application of an electrochemical potential gradient. The model incorporates both the diffusion and drift mechanisms, permitting the evaluation of the contribution of each mechanism. Each mechanism is shown to be dominant depending on the material parameters and the experimental conditions. The results obtained are compatible with experimental and theoretical ones as reported in the literature, suggesting that in several cases studying the transport of mobile species in ionic materials upon the application of an electrochemical potential gradient, the existence of an internal field cannot be ignored. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 4, pp. 398–401. The text was submitted by the authors in English.     

Capillary electrophoretic separation of dsDNA under nonuniform electric fields

Improved sensitivity for the analysis of DNA by capillary electrophoresis has been achieved, based on simultaneous increases in optical path length and injection volume. To increase the optical path length, bubble cells with diameters ranging from 150 to 450 microm have been fabricated and tested. In terms of resolution and sensitivity, a bubble cell of 300 microm diameter is appropriate when using 75-microm capillaries. To allow greater injection volumes, we performed on-line concentration of DNA in the presence of electroosmotic flow (EOF) using 2.0% poly(ethylene oxide) (PEO). With a 300-microm bubble cell, a 170-fold improvement in the sensitivity for the 89-bp fragment has been accomplished when injecting about 0.33 microL DNA. In the presence of the bubble cell, the resolution for the large fragments improves while that for the small ones (<124 base pair) decreases. The effect of bubble cells was further investigated by conducting DNA separation in the absence of EOF, showing that improvements in resolution are mainly due to increased migration differences when DNA migrated at low electric field strengths in the bubble region. We have suggested that such an effect is more profound using shorter capillaries, leading to complete separation of phiX 174 RF DNA-Hae III digest in 2 min.     

kT-scale colloidal interactions in high frequency inhomogeneous AC electric fields. I. Single particles

We report nonintrusive optical microscopy measurements of single micrometer-sized silica and polystyrene colloids in inhomogeneous AC electric fields as a function of field amplitude and frequency. By using a Boltzmann inversion of the time-averaged sampling of single particles within inhomogeneous electric fields, we sensitively measure induced dipole-field interactions on the kT energy scale and fN force scale. Measurements are reported for frequencies when the particle polarizability is greater and less than the medium, as well as the crossover between these conditions when dipole-field interactions vanish. For all cases, the measured interactions are well-described by theoretical potentials by fitting a nondimensional induced dipole-field magnitude. While silica dipole-field magnitudes are well-described by existing electrokinetic models, the polystyrene results suggest an anomalously high surface conductance. Sensitive measurements of dipole-field interactions in this work provide a basis to understand dipole-dipole interactions in particle ensembles in the same measurement geometry in part II.     

Mechanism of rectified lateral motion of particles near electrodes in alternating electric fields below 1 kHz

A rectified electroosmotic flow mechanism and its expression in a quantitative model account for the net lateral motion of colloidal particles above a uniform planar electrode in an alternating electric field that drives a faradaic reaction on the electrode surface. Specific comparison to published particle doublet trajectories at 100 Hz in sodium hydroxide and sodium bicarbonate electrolytes demonstrates that the model quantitatively agrees with the experimental doublet trajectories when only independently measurable parameters are employed. This model reproduces the experimental signatures of the published particle pair motion at 100 Hertz: dependence of the direction of motion on the electrolyte, order of magnitude of the interparticle velocity, invariance of the lateral motion to changes in the particle zeta potential, and observed steady separation between particles that otherwise tend to aggregate. The model is expected to apply up to approximately 1 kHz, at which essentially all of the alternating current flows through the double-layer capacitance and not the faradaic reaction.     

The response of a colloidal suspension to an alternating electric field

This paper is concerned with the calculation of the complex conductivity K* of a suspension, a quantity which may be determined experimentally from the measurement of the alternating current which flows between a pair of electrodes in the suspension due to an alternating voltage difference. A semi-analytic formula is derived for the complex conductivity of a dilute suspension of spherical particles with small dielectric constant which is reasonably accurate for ?-potentials of less than 50 mV. For such suspensions this formula represents a very economical alternative to the exact computer calculation of K* described by DeLacey and White (ref. 2). Although the formula for K* is derived for particles with fixed surface charge, it is shown that the formula can also be applied to a more general class of suspensions, in which the surface charge arises from the dissociation of a single type of surface group.     

Electrokinetics of concentrated suspensions of spherical colloidal particles with surface conductance, arbitrary zeta potential, and double-layer thickness in static electric fields

In this paper the electrophoretic mobility and the electrical conductivity of concentrated suspensions of spherical colloidal particles have been numerically studied under arbitrary conditions including zeta potential, particle volume fraction, double-layer thickness (overlapping of double layers is allowed), surface conductance by a dynamic Stern layer model (DSL), and ionic properties of the solution. We present an extensive set of numerical data of both the electrophoretic mobility and the electrical conductivity versus zeta potential and particle volume fraction, for different electrolyte concentrations. The treatment is based on the use of a cell model to account for hydrodynamic and electrical interactions between particles. Other theoretical approaches have also been considered for comparison. Furthermore, the study includes the possibility of adsorption and lateral motion of ions in the inner region of the double layers (DSL model), according to the theory developed by C. S. Mangelsdorf and L. R. White (J. Chem. Soc. Faraday Trans.86, 2859 (1990)). The results show that the correct limiting cases of low zeta potentials and thin double layers for dilute suspensions are fulfilled by our conductivity formula. Moreover, the presence of a DSL causes very important changes, even dramatic, on the values of both the electrophoretic mobility and the electrical conductivity for a great range of volume fractions and zeta potentials, specially when double layers of adjacent cells overlap, in comparison with the standard case (no Stern layer present). It can be concluded that in general the presence of a dynamic Stern layer causes the electrophoretic mobility to decrease and the electrical conductivity to increase in comparison with the standard case for every volume fraction, zeta potential, and double-layer thickness.     

Aperiodic capillary electrophoresis method using an alternating current electric field for separation of macromolecules

Switching from direct current (DC) to alternating current (AC) electric fields has provided substantial improvements in various instrument techniques that use electric fields for manipulating with various liquid-based systems. For example, AC fields are now used in both light scattering and electroacoustic instruments for measuring xi-potential, largely replacing more traditional microelectrophoresis techniques that use DC fields. In this paper, we suggest a novel way to make a similar transition in the area of separation techniques, capillary electrophoresis (CE) in particular. Dielectrophoresis is one well-known separation effect in which a drifting motion of particles is produced in a "spatially nonhomogeneous" AC electric field. However, there is another field effect that also causes a similar drift of particles. Instead of a "spatially nonhomogeneous" field, this method relies on a "temporally nonhomogeneous" field, normally referred to as "aperiodic electrophoresis". Despite a number of recently published experimental and theoretical papers describing this effect, it is less well-known than dielectrophoresis. We present a short overview of some of the relevant papers. We point out for the first time the idea that "aperiodic electrophoresis" might be useful for separation of macromolecules. We suggest several new mechanisms that could induce this effect in a sufficiently strong AC electric field. This effect can be used as a basis for a new separation method having several important advantages over traditional CE. We present a simple scheme as an example illustrating this new method.     

Controlled deposition of calcium carbonate particles on porous membranes by using alternating current system

The deposition of calcium carbonate particles in the absence of additives was performed through the application of an alternating current. Solutions of calcium chloride and sodium carbonate were filled in glass cells, and a porous polymer membrane was interposed between the glass cells. An alternating current with a sine waveform (frequency: 10 Hz) was applied by using a platinum electrode. In this process, the reciprocal migration of calcium and carbonate ions toward the interface of the pores on the membrane takes place. Moreover, ion mixing occurs to a small extent at the interface of the pores. An alternating current was applied for 30 min during which the ion mixing continued. When observed using a scanning electron microscope, a majority of the formed calcium carbonate particles was found to exhibit a spheroidal vaterite crystal structure. This crystal structure was confirmed to be vaterite after characterization by X-ray diffraction. In the absence of an alternating current, only calcite was formed on the porous polymer membrane. Taking this result into account, it was concluded that the alternating current could induce reciprocal ion migration through the pores of the membrane, and vaterite deposition can be achieved. This is one of the methods employed for the calcium carbonate formation on the porous membrane by using an alternating current system.     

One-, two- and three-dimensional Cu(II) complexes built via new oligopyrazinediamine ligands: from antiferromagnetic to ferromagnetic coupling

Six new pyrazine-modulated N,N'-bis(alpha-pyridyl)-2,6-diaminopyridine ligands (PMN5) were synthesized and their complexes studied. Reaction of copper(II) with the ligand that contained one pyrazine ring in its terminal position led to formation of a one-dimensional zigzag complex whereas copper(II) reactions with ligands containing three pyrazine rings or one pyrazine ring in its middle position yielded straight one-dimensional complexes. A 2-D complex was produced from the ligand with two pyrazine rings at both terminals. When nickel(II) was introduced, a 3-D network was obtained from the three-pyrazine-modulated ligand. Researches on variable-temperature magnetic susceptibility measurements revealed excellent Heisenberg chains with weak antiferromagnetic interaction of J values from -2 to -3 cm(-1)viasigma and pi pathways in straight one-dimensional complexes between the Cu(II) centers separated by 6.8-6.9 A. The zigzag one-dimensional complex showed very poor magnetic coupling. The two-dimensional compound showed significant ferromagnetic interaction in spite of the Cu-Cu distance of 7.2 A. Ferromagnetic coupling was discussed and attributed to the unusual coordination mode of in-plane and out-of-plane linkage of bridging pyrazine rings. The three-dimensional heterometal Cu(II)-Ni(II) compound showed weak antiferromagnetic interaction, which was satisfactorily fitted with J=-2.4 cm(-1) following a one-dimensional theoretical model including MFA.