Rotating Micro-Spheres for adsorption monitoring at a fluid interface.

HYPOTHESIS: A broad range of phenomena, such as emulsification and emulsion stability, foam formation or liquid evaporation, are closely related to the dynamics of adsorbing colloidal particles. Elucidation of the mechanisms implied is key to a correct design of many different types of materials. EXPERIMENTS: Microspheres forced to rotate near a fluid interface exhibit a roto-translational hydrodynamic mechanism that is hindered by capillary torques as soon as the particles protrude the interface. Under these conditions, the time evolution in the ratio of moving spheres provides a direct description of the adsorption kinetics, while microscopy monitoring of particle acceleration\deceleration informs about the adsorption\desorption dynamics. In this work, the proposed strategy is applied at an air/water interface loaded with spherical magnetic particles negatively charged, forced to rotate by the action of a rotating magnetic field. FINDINGS: The proposed method enables the adsorption/desorption dynamics to be followed during the earliest phase of the process, when desorption of a small fraction of particles is detected, as well as to estimate approximated values of the adsorption/desorption constants. The results obtained show that the addition of a monovalent salt or a cationic (anionic) surfactant promotes (inhibits) both adsorption and formation of permanent bonds between particles.

Static and dynamic behavior of magnetic particles at fluid interfaces.

This perspective work reviews the current status of research on magnetic particles at fluid interfaces. The article gives both a unified overview of recent experimental advances and theoretical studies centered on very different phenomena that share a common characteristic: they involve adsorbed magnetic particles that range in size from a few nanometers to several millimeters. Because of their capability of being remotely piloted through controllable external fields, magnetic particles have proven essential as building blocks in the design of new techniques, smart materials and micromachines, with new tunable properties and prospective applications in engineering and biotechnology. Once adsorbed at a fluid-fluid interfase, in a process that can be facilitated via the application of magnetic field gradients, these particles often result sorely confined to two dimensions (2D). In this configuration, inter-particle forces directed along the perpendicular to the interface are typically very small compared to the surface forces. Hence, the confinement and symmetry breaking introduced by the presence of the surface play an important role on the response of the system to the application of an external field. In monolayers of particles where the magnetic is predominant interaction, the states reached are strongly determined by the mode and orientation of the applied field, which promote different patterns and processes. Furthermore, they can reproduce some of the dynamic assemblies displayed in bulk or form new ones, that take advantage of the interfacial phenomena or of the symmetry breaking introduce by the confining boundary. Magnetic colloids are also widely used for unraveling the guiding principles of 2D dynamic self-assembly, in designs devised for producing interface transport, as tiny probes for assessing interfacial rheological properties, neglecting the bulk and inertia contributions, as well as actuated stabilizing agents in foams and emulsions.

Magnetic Biohybrid Vesicles Transported by an Internal Propulsion Mechanism.

Some biological microorganisms can crawl or swim due to coordinated motions of their cytoskeleton or the flagella located inside their bodies, which push the cells forward through intracellular forces. To date, there is no demonstration of synthetic systems propelling at low Reynolds number via the precise actuation of the material confined within an enclosing lipid membrane. Here, we report lipid vesicles and other more complex self-assembled biohybrid structures able to propel due to the advection flows generated by the actuated rotation of the superparamagnetic particles they contain. The proposed swimming and release strategies, based on cooperative hydrodynamic mechanisms and near-infrared laser pulse-triggered destabilization of the phospholipid membranes, open new possibilities for the on-command transport of minute quantities of drugs, fluid or nano-objects. The lipid membranes protect the confined substances from the outside environment during transportation, thus enabling them to work in physiological conditions.

Advances in colloidal manipulation and transport via hydrodynamic interactions.

In this review article, we highlight many recent advances in the field of micromanipulation of colloidal particles using hydrodynamic interactions (HIs), namely solvent mediated long-range interactions. At the micrsocale, the hydrodynamic laws are time reversible and the flow becomes laminar, features that allow precise manipulation and control of colloidal matter. We focus on different strategies where externally operated microstructures generate local flow fields that induce the advection and motion of the surrounding components. In addition, we review cases where the induced flow gives rise to hydrodynamic bound states that may synchronize during the process, a phenomenon essential in different systems such as those that exhibit self-assembly and swarming.

Linear shear rheology of aging ß-casein films adsorbing at the air/water interface.

In this work, the viscoelasticity of fragile ß-casein films has been followed using different macro- and microrheological techniques. The modulus of the complex surface viscosity |η∗| varies with time, allowing for the monitoring of the protein adsorption and annealing. ß-casein adsorption creates a soft glassy gel at the interface that experiences an aging process. Macrorheological experiments with multiple probe sizes in addition to microrheological experiments demonstrated the consistency of the surface rheological properties over a broad range of viscosities. Surface pressure measurements were performed to complement the characterization of the processes.

Magnetic microwire probes for the magnetic rod interfacial stress rheometer.

The magnetic needle interfacial shear rheometer is a valuable tool for the study of the mechanical properties of thin fluid films or monolayers. However, it is difficult to differentiate the interfacial and subphase contributions to the drag on the needle. In principle, the problem can be addressed by decreasing the needle diameter, which decreases the bulk contribution while the interfacial contribution remains essentially the same. Here we show the results obtained when using a new type of needle, that of magnetic microwires with diameter approximately 10 times thinner than for commercial needles. We show that the lower inertia of the microwires calls for a new calibration procedure. We propose such a new calibration procedure based on the flow field solution around the needle introduced in refs 1 and 2. By measuring thin silicone oil films with well-controlled interfacial viscosities as well as eicosanol (C20) and pentadecanoic acid (PDA, C15) Langmuir monolayers, we show that the new calibration method works well for standard needles as well as for the microwire probes. Moreover, we show that the analysis of the force terms contributing to the force on the needle helps to ascertain whether the measurements obtained are reliable for given surface shear viscosity values. We also show that the microwire probes have at least a 10-fold-lower resolution limit, allowing one to measure interfacial viscosities as low as 10(-7) N·m/s.

Field-induced sublimation in perfect two-dimensional colloidal crystals.

Phase transitions in two-dimensional (2D) systems are of considerable fundamental and practical importance. However, the kinetics of these processes are difficult to predict and understand, even in simple systems for which equilibrium states are properly described, owing to the difficulty of studying crystallites with single-particle resolution and free of defects. Here we introduce an alternative method for the sublimation of 2D colloidal crystallites by a sudden induction of repulsive forces between the particles. The sublimation kinetics, studied in real space by microscopy and by computer simulations, shows a scaling behavior that suggests a universal mechanism fundamentally different from the one usually accepted for thermal sublimation. The universal behavior found for the early stages of the process may be useful for understanding the dynamic features of particle systems at liquid interfaces and for designing technological applications without the need of performing extensive experimental studies.

Phase behavior of dense colloidal binary monolayers.

In this work, we study how structures develop on 2D dense binary colloidal monolayers as a function of the relative concentration of small/large particles. Translational and orientational distribution functions have been used to monitor the continuous phase transition through a detailed characterization of the global and local order. We have observed how a gradual enhancement in the number of particles of different sizes leads to a continuous vitrification process and how homogeneous binary glasses form in equimolar mixtures. Also, we have performed a simple calculation that relates the structures found to the pair dipolar potential, allowing the forecast of local structures in other arbitrary binary mixtures. Finally, we have corroborated the goodness of the binary systems as a glass-forming model by comparing the established scenario with the structural features found in partially aggregated monolayers.

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.