Magnetic susceptibility of concentrated ferrocolloids

The initial susceptibility of ferrocolloids (magnetic fluids) is studied within wide ranges of temperature and concentration. Experimental results are compared with the predictions of current theoretical models. A modified formula is proposed for an equilibrium ferrocolloid susceptibility, which allowed us to obtain quantitative agreement with the experimental data. It is shown that magnetodipole interparticle interactions lead to a manyfold increase in the susceptibility; however, no evidence of the spontaneous transition of ferrocolloids to the magnetoordered state are disclosed. For ferrocolloids with a dispersion medium having a low melting point, the loss of fluidity and transition to the solidified state at temperatures above the melting point are revealed. The independence of the solidification temperature on the magnetic phase concentration and strong temperature dependence on the type of stabilizer make it possible to suggest that the transition is associated with molecular interactions. The solidification of a magnetic fluid is accompanied by the appearance of a peak on the temperature dependence of susceptibility in all cases when large particles are present in a colloidal solution, and the relaxation of particle magnetic moment is due to thermal motion of the particles.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 218–230.Original Russian Text Copyright © 2005 by Pshenichnikov, Lebedev.     

Magnetophoresis, sedimentation, and diffusion of particles in concentrated magnetic fluids

A dynamic mass transfer equation for describing magnetophoresis, sedimentation, and gradient diffusion of colloidal particles in concentrated magnetic fluids has been derived. This equation takes into account steric, magnetodipole, and hydrodynamic interparticle interactions. Steric interactions have been investigated using the Carnahan-Starling approximation for a hard-sphere system. In order to study the effective interparticle attraction, the free energy of the dipolar hard-sphere system is represented as a virial expansion with accuracy to the terms quadratic in particle concentration. The virial expansion gives an interpolation formula that fits well the results of computer simulation in a wide range of particle concentrations and interparticle interaction energies. The diffusion coefficient of colloidal particles is written with regard to steric, magnetodipole and hydrodynamic interactions. We thereby laid the foundation for the formulation of boundary-value problems and for calculation of concentration and magnetic fields in the devices (for example, magnetic fluid seals and acceleration sensors), which use a concentrated magnetic fluid as a working fluid. The Monte-Carlo methods and the analytical approach are employed to study the magnetic fluid stratification generated by the gravitational field in a cylinder of finite height. The coefficient of concentration stratification of the magnetic fluid is calculated in relation to the average concentration of particles and the dipolar coupling constant. It is shown that the effective particle attraction causes a many-fold increase in the concentration inhomogeneity of the fluid if the average volume fraction of particles does not exceed 30%. At high volume concentrations steric interactions play a crucial role.     

Dipole interparticle interaction in magnetic fluids

The temperature dependence of the saturation magnetization of a magnetite-based magnetic fluid has been directly measured with a vibrating-coil magnetometer equipped with a superconducting solenoid. The magnetization varies in accordance with the 1 ? αT ² law. Coefficient α = 1.4 × 10^?6 is almost twice as high as that of monolithic magnetite. The results of measuring the susceptibility of magnetic fluids stabilized with oleic and linoleic acids have been analyzed using novel corrections to the temperature dependence of particle magnetization. The susceptibility of ultimately concentrated samples is in good agreement with the Ivanov-Huke-Lücke and Morozov theories. The susceptibility of samples with a medium concentration is adequately described by the Ivanov theory alone. The susceptibility of low-concentrated samples increases to the level predicted by the Morozov theory in the case of particle aggregation. The widening of the particle size distribution leads to a reduction in the level of the interparticle interactions.     

磁流变液组分对其沉降性影响的研究进展

磁流变液是一种形态和性能受外加磁场控制的新型智能材料。在汽车、建筑、医疗、航空航天多种领域具有重要的应用价值,但磁流变液沉降性问题一直是影响其广泛应用的难题。因此,首先从载液、磁性颗粒和添加剂三方面出发,简要回顾了近几年在磁流变液沉降性方面的研究,指出了影响磁流变液沉降性的因素主要有：载液的粘度、磁性颗粒的形状和尺寸、磁性颗粒与载液之间的密度差、添加剂的种类与添加量等。并给出了有效提高磁流变液沉降性的可行策略,最后从磁流变液的沉降现象与应用方面对沉降性研究进行了展望。     

Communication: Generalizing Rosenfeld's excess-entropy scaling to predict long-time diffusivity in dense fluids of Brownian particles: from hard to ultrasoft interactions

Computer simulations are used to test whether a recently introduced generalization of Rosenfeld's excess-entropy scaling method for estimating transport coefficients in systems obeying molecular dynamics can be extended to predict long-time diffusivities in fluids of particles undergoing Brownian dynamics in the absence of interparticle hydrodynamic forces. Model fluids with inverse-power-law, Gaussian-core, and Hertzian pair interactions are considered. Within the generalized Rosenfeld scaling method, long-time diffusivities of ultrasoft Gaussian-core and Hertzian particle fluids, which display anomalous trends with increasing density, are predicted (to within 20%) based on knowledge of interparticle interactions, excess entropy, and scaling behavior of simpler inverse-power-law fluids.     

Dispersion of magnetic susceptibility and the microstructure of magnetic fluid

The microstructure of magnetic fluid produced on the basis of kerosene with oleic acid as a stabilizer is studied experimentally. An analytical procedure based on the known dependence of the time of Brownian relaxation of the magnetic moment of the colloidal particle on its size and the expansion of a low-frequency spectrum of dynamic susceptibility into the series of Debye functions is used. Magnetic susceptibility is measured at frequencies from 10 Hz to 100 kHz and temperatures from 225 to 360 K for colloidal solutions with the volume fraction of magnetite from 0.08 to 0.17. The clusters with uncompensated magnetic moments and sizes varying from 50 to 70 nm that are three-or fourfold larger than the mean diameter of a single colloidal particle are found. It is revealed that characteristic sizes of clusters are virtually independent of temperature and concentration of colloidal particles. The contribution of clusters to the equilibrium susceptibility of magnetic fluid grows exponentially with decreasing temperature, being manyfold larger at low temperatures than that of single particles. The obtained temperature dependence of equilibrium susceptibility is compared with that predicted from current theoretical models.     

Linear Orientational Magnetodynamics of a Ferrogel

The dynamics of magnetization is theoretically studied for a system of ferromagnetic nanoparticles suspended in a gel (a ferrogel). The Brownian motion impedes orientation of the particles determined by the elastic matrix. Therefore, the main parameter of the medium determining the static magnetic susceptibility value is the ratio of the modulus of elasticity of matrix to the temperature. The dispersion factors of dynamic susceptibility components include combinations of the velocities of several processes: elastic restoration of the orientation of particles, their rotational Brownian diffusion, and viscous relaxation of the inertial motion. The absorption of the energy of the alternating field in a ferrogel is found to be lower than in an isotropic magnetic suspension. The effect of the interaction of elastic and Brownian forces on the effective times of ferrogel magnetization relaxation is monitored.     

Thermodynamic and structural properties of confined discrete-potential fluids

The thermodynamic and structural behaviors of confined discrete-potential fluids are analyzed by computer simulations, studying in a systematic way the effects observed by varying the density, temperature, and parameters of the potentials that characterize the molecule-molecule interactions. The Gibbs ensemble simulation technique for confined fluids [A. Z. Panagiotopoulos, Mol. Phys. 62, 701 (1987)] is applied to a fluid confined between two parallel hard walls. Two different systems have been considered, both formed by spherical particles that differ by the interparticle pair potential: a square well plus square shoulder or a square shoulder plus square well interaction. These model interactions can describe in an effective way pair potentials of real molecular and colloidal systems. Results are compared with the simpler reference systems of square-shoulder and square-well fluids, both under confinement. From the adsorption characterization through the use of density profiles, it is possible to obtain specific values of the interparticle potential parameters that result in a positive to negative adsorption transition.     

Interparticle interactions in agglomerates of alpha-Fe2O3 nanoparticles: influence of grinding

We have chemically prepared a sample of antiferromagnetic alpha-Fe2O3 nanoparticles by a gel-sol technique. M?ssbauer spectra of the as-prepared sample showed that superparamagnetic relaxation was suppressed due to strong magnetic interparticle interactions even at room temperature. However, subsequent grinding of the sample by hand in a mortar for some minutes resulted in fast superparamagnetic relaxation of some of the particles. The effect was even more dramatic if the alpha-Fe2O3 powder was ground for a longer time or together with nonmagnetic eta-Al2O3 nanoparticles. Similar effects were found after low-energy ball milling. Thus it is found that the agglomeration of the nanoparticles during preparation under wet conditions results in strong magnetic interparticle interaction, but a relatively gentle mechanical treatment is sufficient to break up the agglomerates, resulting in much weaker interactions. We show that these effects can also be seen when a soil sample containing magnetic nanoparticles is ground.     

Mesoscale constitutive modeling of magnetic dispersions

A constitutive model for dispersions of acicular magnetic particles has been developed by modeling the particles as rigid dumbbells dispersed in a solvent. The effects of Brownian motion, anisotropic hydrodynamic drag, a steric force in the form of the Maier-Saupe potential, and, most importantly, a mean-field magnetic potential are included in the model. The development is similar to previous models for liquid-crystalline polymers. The model predicts multiple orientational states for the dispersion, and this phase behavior is described in terms of an orientational order parameter S and an average alignment parameter J; the latter is introduced because the magnetic particles have distinguishable direction due to polarity. A transition from isotropic to nematic phases at equilibrium is predicted. Multiple nematic phases-both prolate and oblate-are predicted in the presence of steady shear flow and external magnetic field parallel to the flow. The effect of increasing magnetic interparticle interactions and particle concentration is also presented. Comparisons with experimental data for the steady shear viscosity show very good agreement.     

Size-sorted anionic iron oxide nanomagnets as colloidal mediators for magnetic hyperthermia

Iron oxide colloidal nanomagnets generate heat when subjected to an alternating magnetic field. Their heating power, governed by the mechanisms of magnetic energy dissipation for single-domain particles (Brown and Néel relaxations), is highly sensitive to the crystal size, the material, and the solvent properties. This study was designed to distinguish between the contributions of Néel and Brownian mechanisms to heat generation. Anionic nanocrystals of maghemite and cobalt ferrite, differing by their magnetic anisotropy, were chemically synthesized and dispersed in an aqueous suspension by electrostatic stabilization. The particles were size-sorted by successive electrostatic phase separation steps. Parameters governing the efficiency of nanomagnets as heat mediators were varied independently; these comprised the particle size (from 5 to 16.5 nm), the solvent viscosity, magnetic anisotropy, and the magnetic field frequency and amplitude. The measured specific loss powers (SLPs) were in quantitative agreement with the results of a predictive model taking into account both Néel and Brown loss processes and the whole particle size distribution. By varying the carrier fluid viscosity, we found that Brownian friction within the carrier fluid was the main contributor to the heating power of cobalt ferrite particles. In contrast, Néel internal rotation of the magnetic moment accounted for most of the loss power of maghemite particles. Specific loss powers were varied by 3 orders of magnitude with increasing maghemite crystal size (from 4 to 1650 W/g at 700 kHz and 24.8 kA/m). This comprehensive parametric study provides the groundwork for the use of anionic colloidal nanocrystals to generate magnetically induced hyperthermia in various media, including complex systems and biological materials.     

Dynamical density functional theory and its application to spinodal decomposition

We present an alternative derivation of the dynamical density functional theory for the one-body density profile of a classical fluid developed by Marconi and Tarazona [J. Chem. Phys. 110, 8032 (1999)]. Our derivation elucidates further some of the physical assumptions inherent in the theory and shows that it is not restricted to fluids composed of particles interacting solely via pair potentials; rather it applies to general, multibody interactions. The starting point for our derivation is the Smoluchowski equation and the theory is therefore one for Brownian particles and as such is applicable to colloidal fluids. In the second part of this paper we use the dynamical density functional theory to derive a theory for spinodal decomposition that is applicable at both early and intermediate times. For early stages of spinodal decomposition our nonlinear theory is equivalent to the (generalized) linear Cahn-Hilliard theory, but for later times it incorporates coupling between different Fourier components of the density fluctuations (modes) and therefore goes beyond Cahn-Hilliard theory. We describe the results of calculations for a model (Yukawa) fluid which show that the coupling leads to the growth of a second maximum in the density fluctuations, at a wave number larger than that of the main peak.     

Structure of electrorheological fluids under an electric field and a shear flow: experiment and computer simulation

It is known that macroscopic properties of colloidal suspensions are often determined by the microstructure of the particles in the suspensions, depending on the interparticle, Brownian, and hydrodynamic (if any) forces. We take electrorheological (ER) fluids as an example. By using a computer simulation and an experimental approach, we investigate the structure of ER fluids subjected to both an electric field and a shear flow. The microstructure evolution from random structure, to chains, and then to stable lamellar patterns, observed in the experiments, agrees very well with that obtained in the simulations. It is shown that the formation of such lamellar patterns originates from the difference between the dipole moment induced in the particles suspended in the ER fluids without shear and the one with shear. The results on the relaxation process of structural formation and the internal structure of layers are also presented. Thus, it seems possible to achieve various structures and hence desired macroscopic properties of colloidal suspensions by adjusting external fields and, simultaneously, a shear flow.     

Cluster formation in two-Yukawa fluids

We present a different and efficient method for implementing the analytical solution of Ornstein-Zernike equation for two-Yukawa fluids in the mean spherical approximation. We investigate, in particular, the conditions for the formation of an extra low-Q peak in the structure factor, which we interpret as due to cluster formation in the two-Yukawa fluid when the interparticle potential is composed of a short-range attraction and a long-range repulsion. We then apply this model to interpret the small angle neutron scattering data for protein solutions at moderate concentrations and find out that the presence of a peak centered at Q=0 (zero-Q peak) besides the regular interaction peak due to charged proteins implies an existence of long-range attractive interactions besides the charge repulsion.     

Study on the properties and stability of ionic liquid-based ferrofluids

Ionic liquid (IL)-based ferrofluids have been prepared dispersing both bare and sterically stabilized CoFe₂O₄ nanoparticles. The precipitated particles were characterized by X-ray diffraction, scanning electronic microscopy, transmission electron microscopy, Fourier transform infrared, and vibrating sample magnetometry studies. The water-absorbing property of ferrofluids at ambient temperature was estimated by weight and viscosity measurements. Colloidal dispersion stability of the ferrofluids was evaluated by particle suspension percentage. Experimental results indicate that interparticle electrostatic repulsion is not effective in stabilizing bare magnetic particles in IL. There is no significant increase on the dispersion stability when the particles were coated with a monolayer of oleic acid. The reason could be caused by the incompatibility between the nonpolar tail of surfactant and carrier liquid. When excess oleic acid was added into IL, stable magnetic colloid was achieved by a steric stabilization layer coated to be compatible with the IL.     

Experimental study of isopycnic focusing generated by coupled electric and gravitational field forces: Use in thin layer focusing and focusing field-flow fractionation

Various operational parameters affecting the formation of the density gradient generated by the electric field action on a binary pseudo-continuous carrier liquid composed of charged colloidal silica particles suspended in water and the isopycnic focusing of sample particles were investigated under conditions of static thin layer focusing and dynamic focusing field-flow fractionation. The properties and the behavior of the density gradient forming carrier liquid were studied. The experimental results are compared with theoretical predictions and discussed with respect to potential applications of the proposed concept not only for separation purposes but also for studies of interparticle interactions.     

Control of particle assisted wetting by an external magnetic field

It is shown that repulsive particles can assist wetting of a water surface by an organic liquid even at a particle density substantially less than a close packed monolayer. By applying external fields, one can change the interparticle interactions from net attractive to net repulsive and thus induce a transition from nonwetting to wetting conditions. This was achieved by applying superparamagnetic polystyrene particles together with a polymerizable organic liquid (trimethylolpropane trimethacrylate) to a water surface in the middle of a solenoid. Passing a current through the solenoid created a magnetic field perpendicular to the interface that polarized the particles and induced repulsive dipole-dipole forces. Without the field, lenses of the organic liquid that included aggregates of particles floating on the water surface were observed. In the presence of the field, the organic liquid and the particles were evenly distributed across the surface. The interparticle distance increases proportional to the square root of the area per particle and is close to the value expected for hexagonal order.     

On Nonlinear Orientational Effects in the Ferrocolloid Rotating in a Magnetic Field

The orientational dynamics of a system of noninteracting hard-magnetic ferroparticles in a fluid matrix rotating in a transverse magnetic field small as compared with the effective anisotropy field of a particle was considered. The problem of the dynamics of an individual particle with a magnetic moment incompletely frozen in the crystalline matrix was solved. An orientational microkinetic equation was formulated with allowances made for the Brownian motion of particles for high rotation frequencies. It was established that the presence of a small orientational freedom of the moment in the particle body dramatically changes the behavior of the system. A particular result is a giant retardation of the mechanical and magnetic orientational relaxation in the colloid preliminary magnetized along the rotation axis.     

Nature of the breakdown in the Stokes-Einstein relationship in a hard sphere fluid

Molecular dynamics simulations of high density hard sphere fluids clearly show a breakdown of the Stokes-Einstein equation (SE). This result has been conjectured to be due to the presence of mobile particles, i.e., ones which have the propensity to "hop" distances that are integer multiples of the interparticle distance. We conclusively show that the sedentary particles, i.e., ones complementary to the "hoppers," obey the SE relationship to a good approximation, even though the fluid as a whole violates the SE equation at high densities. These results support the notion that the unusual diffusive behavior of supercooled liquids is dominated by the hopping particles.     

Strong magnetic field effects on solid-liquid and particle-particle interactions during the processing of a conducting liquid containing non-conducting particles

The behavior of micrometer-sized weak magnetic insulating particles migrating in a conductive liquid metal is of broad interest during strong magnetic field processing of materials. In the present paper, we develop a numerical method to investigate the solid-liquid and particle-particle interactions by using a computational fluid dynamics (CFDs) modeling. By applying a strong magnetic field, for example, 10 Tesla, the drag forces of a single spherical particle can be increased up to around 15% at a creeping flow limit. However, magnetic field effects are reduced when the Reynolds number becomes higher. For two identical particles migrating along their centerline in a conductive liquid, both the drag forces and the magnetic interaction will be influenced. Factors such as interparticle distance, Reynolds number and magnetic flux density are investigated. Shielding effects are found from the leading particle, which will subsequently induce a hydrodynamic interaction between two particles. Strong magnetic fields however do not appear to have a significant influence on the shielding effects. In addition, the magnetic interaction forces of magnetic dipole-dipole interaction and induced magneto-hydrodynamic interaction are considered. It can be found that the induced magneto-hydrodynamic interaction force highly depends on the flow field and magnetic flux density. Therefore, the interaction between insulating particles can be controlled by applying a strong magnetic field and modifying the flow field. The present research provides a better understanding of the magnetic field induced interaction during liquid metal processing, and a method of non-metallic particles manipulation for metal/ceramic based materials preparation may be proposed.