Primary and secondary bonds in field induced aggregation of electric double layered magnetic particles.

Magnetic filaments able to survive on removal of the magnetic field have led to new applications in biotechnology and microfluidics. In this work, the stability of linear field induced aggregates composed of electric double layered magnetic particles has been studied in the framework of the DLVO theory. A suitable system of differential equations is proposed in order to determine how the percentage of bonds formed in a primary or a secondary energy minimum depends on the exposure time to the magnetic field. The theoretical predictions were compared with experimental data obtained by means of dynamic light scattering. The aggregation experiments were performed at different electrolyte concentrations and exposure times to the magnetic field. Fitting the experimental results according to the proposed theory allowed us to determine the rate at which bonds formed in a secondary energy minimum turn into stable bonds.

Kinetic study of coupled field-induced aggregation and sedimentation processes arising in magnetic fluids.

In this work, the kinetics of coupled aggregation and sedimentation processes arising in magnetic fluids has been studied. Aggregation was induced applying a constant uniaxial magnetic field. The time evolution of the cluster-size distribution and the weight-average chain length was monitored using optical microscopy and digital image analysis. The experimental results are compared with the corresponding solutions of Smoluchowski's equation. For this purpose, a recently proposed aggregation kernel was employed. When sedimentation effects are taken into account, the fits improve especially at long aggregation times.

Controlling the magnetic filaments length by tuning the particle interactions.

Initially stable samples of monodisperse superparamagnetic particles were aggregated in the presence of an external magnetic field and different amounts of electrolyte. The aggregation process was monitored using dynamic light scattering (DLS). When the magnetic field was turned off, a significant change of the effective diffusion coefficient was observed at all electrolyte concentrations. This jump was interpreted in terms of filament break-up and additional rotational diffusive modes. Therefore, the length of the magnetic filaments (MF) was determined from the measured average diffusion coefficients applying an adequate theoretical approach. The results prove that the MFs disassemble completely at low electrolyte concentrations. At intermediate amounts of electrolyte added, a partial cluster break-up is observed. Only at high salt concentrations, the chains withstand the absence of the magnetic field. The results show that average filament size can be predicted and controlled by tuning the relative strength of the magnetic and electric interactions.

Formation of magnetic filaments: a kinetic study.

In order to form magnetic filaments or chains, aqueous suspensions of superparamagnetic colloidal particles were aggregated under the action of an external magnetic field in the presence of different amounts of an indifferent 1:1 electrolyte (KBr). This allowed the influence of the anisotropic magnetic and isotropic electrostatic interactions on the aggregation behavior of these electric double-layered magnetic particles to be studied. Dynamic light scattering was used for monitoring the average diffusion coefficient of the magnetic filaments formed. Hydrodynamic equations were employed for obtaining the average chain lengths from the experimental mean diffusion coefficients. The results show that, for the same exposure time to the magnetic field, the average filament size is monotonously related to the amount of electrolyte added. The chain growth behavior was found to follow a power law with a similar exponent for all electrolyte concentrations used in this work. The time evolution of the average filament size can be rescaled such that all the curves collapse on a single master curve. Since the electrolyte added does not have any effect on the scaling behavior, the mechanism of aggregation seems to be completely controlled by the dipolar interaction. However, electrolyte addition not only controls the range of the total interaction between the particles, but also enhances the growth rate of the aggregation process. Taking into account the anisotropic character of these aggregation processes we propose a kernel that depends explicitly on the range of the dipolar interaction. The corresponding solutions of the Smoluchowski equation combined with theoretical models for the diffusion and light scattering by rigid rods reproduce the measured time evolution of the average perpendicular aggregate diffusion coefficient quite satisfactorily.

Forming chainlike filaments of magnetic colloids: the role of the relative strength of isotropic and anisotropic particle interactions.

The influence of the interplay between anisotropic magnetic and isotropic electrostatic interactions on the aggregation behavior of aqueous suspensions of electric double layered magnetic particles was studied. Therefore, the particles were aggregated under the action of an external magnetic field and in the presence of different amounts of an indifferent 1:1 electrolyte. After removing the field, linear aggregates remained in the sample. Static light scattering and electron micrographs confirmed the chainlike cluster morphology. Dynamic light scattering was used for monitoring the average diffusion coefficient of these magnetic filaments. A theoretical model that allows the experimental mean diffusion coefficient to be related to the average chain length was successfully employed. The results show that, at fixed exposure time and field strength, the average filament size is proportional to the amount of electrolyte added. The light scattering data and transmission electron microscopy micrographs prove that permanent chains coexist with a relatively large fraction of individual particles when no or little electrolyte was added to the samples. A plausible explanation for this "selective aggregation" phenomenon could be given in terms of surface charge heterogeneities. The chain growth was found to follow a power law with a similar exponent for all the electrolyte concentrations studied. Scaling theories were employed for estimating the ratio of particles taking part in the aggregation process.

Modeling the aggregation of partially covered particles: theory and simulation.

A theoretical model for describing the initial stages of the aggregation of partially covered colloidal particles is presented. It is based on the assumption of short-range interactions that may be modeled by a sticking probability on contact. Three types of sticking probabilities are distinguished depending on the collision type, i.e., for bare-bare, bare-covered, and covered-covered collisions. Hence, the model allows an analytical expression for the dimer-formation rate constant k(11), to be deduced as a function of the degree of surface coverage and the three sticking probabilities. The theoretical predictions are contrasted with simulated data. The observed agreement between theory and simulations shows the usefulness of the model for predicting the initial stages of this kind of aggregation processes.

Effective charges of colloidal particles obtained from collective diffusion experiments.

In this work, the collective diffusion coefficient of highly charged colloidal particles in dilute dispersions has been measured by means of dynamic light scattering. The possibility of obtaining valuable information about the particle charge from these data is looked into with the help of electrophoresis experiments. Our results suggest that this is possible in the case of slight or moderately interacting particles as long as experimental data are properly treated. For highly interacting colloids, however, such information could not be so reliable, presumably due to certain shortcomings of the experimental technique at low angle. The role of charge renormalization is also discussed in this work.

Clustering under short-range finite interactions.

In this paper the aggregation of surface modified colloidal particles is presented, paying special attention to the cluster structure and growth. The surface was modified by adsorbing bovine serum albumin (BSA). The interaction potential develops a minimum of restricted depth, weakening the clusters which subsequently restructure and form more compact morphologies. This minimum is responsible for the reversibility of the aggregation processes (this is an important difference between diffusion-limited cluster aggregation and reaction-limited cluster aggregation). The energy minimum is associated with the presence of a steric term in the energy balance, which depends on the size of the adsorbed molecules. BSA molecules with different sizes were employed to test this point. In addition, the short-range interaction seems not to affect significantly the paths of approximating particles, since the aggregation of the clusters at long times is independent of the size of these particles. The long-time kinetics was interpreted in the frame of dynamic scaling concepts. A kinetics model, including surface-surface, protein-surface, and protein-protein aggregation, is used to determine the dominant mechanism controlling the aggregation.

A Light Scattering Study of the Transition Region between Diffusion- and Reaction-Limited Cluster Aggregation.

Two limiting regimes for colloidal particle aggregation are well described in the literature: diffusion-limited cluster aggregation and reaction-limited cluster aggregation. Between these two limiting regimes, a vast transition region is expected. In this paper, the transition region is studied by means of static and dynamic light scattering. Therefore, a system of latex particles is aggregated at different electrolyte concentrations. The time dependence of the average diffusion coefficient is fitted considering the Brownian kernel and the kernel proposed by Schmitt et al. [Phys. Rev. E 62, 8335 (2000)]. The first fits the experimental data only at high electrolyte concentrations while the latter, which considers multiple cluster-cluster contacts, is found to fit the complete set of experimental data. Copyright 2001 Academic Press.