Colloids on the frontier of ferrofluids. Rheological properties

This paper is devoted to the steady-state rheological properties of two new kinds of ferrofluids. One of these was constituted by CoNi nanospheres of 24 nm in diameter, whereas the other by CoNi nanofibers of 56 nm in length and 6.6 nm in width. These ferrofluids were subjected to shear rate ramps under the presence of magnetic fields of different intensity, and the corresponding shear stress values were measured. From the obtained rheograms (shear stress vs shear rate curves) the values of both the static and the dynamic yield stresses were obtained as a function of the magnetic field. The magnetoviscous effect was also obtained as a function of both the shear rate and the magnetic field. The experimental results demonstrate that upon magnetic field application these new ferrofluids develop yield stresses and magnetoviscous effects much greater than those of conventional ferrofluids, based on nanospheres of approximately 10 nm in diameter. Besides some expected differences, such as the stronger magnetorheological effect in the case of ferrofluids based on nanofibers, some intriguing differences are found between the rheological behaviors of nanofiber ferrofluids and nanosphere ferrofluid. First, upon field application the rheograms of nanofiber ferrofluids present N-shaped dependence of the shear stress on the shear rate. The decreasing part of the rheograms takes place at low shear rate. These regions of negative differential viscosity, and therefore, unstable flow is not observed in the case of nanosphere ferrofluids. The second intriguing difference concerns the curvature of the yield stress vs magnetic field curves. This curvature is negative in the case of nanosphere ferrofluid, giving rise to saturation of the yield stress at medium field, as expected. However, in the case of nanofiber ferrofluid this curvature is positive, which means a faster increase of the yield stress with the magnetic field the higher the magnitude of the latter. These interesting differences may be due to the existence of strong interparticle solid friction in the case of nanofiber ferrofluids. Finally, theoretical models for the static yield stress of the ferrofluids were developed. These models consider that upon field application the ferrofluid nanoparticles are condensed in drops of dense phase. These drops tend to be aligned along the field direction, opposing the flow of the ferrofluids and being responsible for the static quasielastic deformation and the yield-stress phenomena. By considering the existence of interparticle dry friction only in the case of nanofiber ferrofluids, the developed models predicted quite well not only the magnitude of the static yield stress but also the differences in curvature of the yield stress vs magnetic field curves.     

微流控芯片中颗粒/细胞磁操控的研究进展

微流控芯片中颗粒/细胞的磁操控是当前的热点研究领域.本文详细介绍了微流控芯片中颗粒/细胞磁操控原理及几种主要操控方式,包括分离、集中、捕获与排列组装.其中,基于颗粒/细胞大小、形状以及有无磁性对分离方法展开详述.此外,本文还比较了通道几何结构、磁场强度及分布、磁性液体种类(顺磁盐溶液和磁流体)对操控性能的影响.最后,针对微流控芯片中颗粒/细胞磁操控的前景进行了展望.     

Surface modification of iron oxide nanoparticles by a phosphate‐based macromonomer and further encapsulation into submicrometer polystyrene particles by miniemulsion polymerization

A new strategy relying on the use of a phosphate‐based macromonomer (PAM200) to modify the surface of iron oxide nanoparticles was developed for the synthesis of submicrometer polystyrene (PS) magnetic particles. First, iron oxide nanoparticles were synthesized using the coprecipitation of ferrous and ferric salts in alkaline medium. Besides the classical oleic acid (OA)/octane‐based ferrofluid, styrene‐based ferrofluids were elaborated with either OA or PAM200 as the stabilizer. In all cases, maghemite (γ‐Fe₂O₃) was clearly identified, with nanoparticles rather spherical in shape but exhibiting broad particle size distribution (PSD). Both OA and PAM200 led to stable maghemite‐based ferrofluids showing superparamagnetic properties. Further use of these ferrofluids in styrene miniemulsion polymerization resulted in inhomogeneous distribution of maghemite among and inside the polymer particles with OA‐based ferrofluids, whereas PAM200/styrene‐based ferrofluids led to magnetic particles with homogeneous distribution of maghemite inside PS particles. Broad PSD and small nonmagnetic particles were however observed. The true mechanisms operating in these systems are still to elucidate, but this study validates PAM200 as an efficient compatibilizing agent between hydrophilic maghemite and hydrophobic PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 327–340, 2008     

Preparation of PMAA-coated Dysprosium Ferrite Ferrofluids and Study on the Superparamagnetism

IntroductionFerrofluids[1] consistof ultramicroscopic ferro-and ferrimagnetic particles coated with a monolayeror a bilayer of surfactant molecules,which are col-loidally dispersed in a carrier liquid.Under the in-fluence of an external magnetic field,such ferroflu-ids exhibit certain novel phenomena and severalphysical properties of theirs are modified.For ex-ample,ferrofluids are stable in the gravitationaland magnetic fields and behave not only as solidshaving a large saturation magnetizati…     

Structure of Chain Aggregates in Ferrocolloids

The structure of chain aggregates in polydisperse ferrocolloids is considered. The chain distribution over the number of constituent particles is investigated on the basis of the method of heterophase fluctuations. The polydispersity of ferrofluids is taken into account within the frameworks of two-fraction model suggesting the presence of a large number of small particles and a small number of large particles. The sorting algorithm of chain structures with various energies is presented. It is shown that, in real ferrofluids, the most probable are the chains composed of large particles with one or two small particles at the edges. The model predicts that the most of large particles are bonded into short chain aggregates whose average length consists of two or three particles at room temperature.     

Magnetic Latex Particles in Nanobiotechnologies for Biomedical Diagnostic Applications: State of the Art

Summary: The main objective of this short state-of-the art is to report on the preparation of reactive magnetic latexes for biomedical applications. The main advantage of colloidal magnetic particles is their separation upon applying an external permanent magnetic field. Then magnetic particles bearing reactive groups or specific receptors are used in biomedical diagnosis such as immunoassay, molecular diagnosis for specific capture and detection of nucleic acids, viruses extraction and detection, cell sorting and more recently in numerous biotechnological applications. The preparation of magnetic latexes requires the use of well-defined iron oxide nanoparticles in appropriate medium. In this direction, aqueous ferrofluids were largely used to prepare functional magnetic latexes, whereas few approaches have been devoted to the use of organic ferrofluids.     

Magnetorheological properties of ferrofluids containing clustered particles

A theoretical model is proposed to describe experimental data on the magnetorheological properties of magnetic fluids containing clustered particles consisting of single-domain ferromagnetic nanoparticles distributed in a polymeric shell 80–100 nm in diameter. These fluids combine the sedimentation stability typical of nanodisperse ferrofluids with the high sensitivity of rheological parameters to magnetic fields. The developed model explains the experimentally found long-term rheological relaxation and residual stress that is retained after the medium ceases to flow.     

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.     

Saturation Magnetization and Law of Approach to Saturation for Self-formed Ionic Ferrofluids Based on MnFe2O2 Nanoparticles

The magnetization curves of MnFe₂O₂ nanoparticles and self-formed ferrofluids based on these particles have been measured at room temperature. The median size of the particlesis 13.67 nm. The specific saturation magnetization is less than the theoretical value for theferrofluids. In the high field range from 5 kOe to 10 kOe, the higher the particle volume fraction is, the steeper the slope of the magnetization curves is when it approaches saturation.The behavior of the saturation magnetization and the law of approach to saturation are due to the presence of self-assembled aggregates of ring-like micelle structures which form in the absence of the magnetic field and field-induced aggregates, respectively. The field-induced aggregates have a dissipative structure, so that at high field, the law of approach to saturation magnetization is different from the one described using Langevin paramagnetism theory. The large particles in the ferrofluids result in apparent hysteresis.     

Preparation of Dy‐ferrite Ferrofluids and Magnetochemical Studies on the Superparamagnetism

This paper reports unprecedented preparation of Dy‐ferrite water‐based ferrofluids stabilized by polymeric surfactant PMAA. The stability of ferrofluids was characterized in terms of the equation of criterion for the stability of ferrofluids. Magnetic susceptibility was measured with a Faraday‐type magnetic balance at different temperature and with different magnetic field intensity. According to the Langevin function, superparamagnetism of Dy‐ferrite ferrofluids has been confirmed by the curves of saturation magnetization σ versus H/ T, and the blocking temperature is between 160 and 200 K. In terms of the simplified Langevin function in the low magnetic field, the average particle size is 20 nm that coincides with the result evaluated by FHMW. In addition, chemical analysis, infrared spectra and Mossbauer spectroscopy were utilized to analyze the main components of the ferrofluids.     

Diffusion and magnetotransport in ferrofluids containing chain-shaped aggregates

The effect of chain structures on particle diffusion in nanodisperse ferrofluids subjected to external magnetic fields is studied. It is shown that the chain formation imparts very strong anisotropy to the diffusion properties of ferrofluids: the diffusion coefficient along a field appears to be approximately two orders of magnitude higher than that in the transverse direction. The presence of the chains changes the particle magnetophoresis coefficient significantly.     

广义簇合物在均匀几率密度场下的生长

通过对广义簇合物生长的自调整模型的解析,得出了粒子在均匀几率密度场下簇合物生长形态的变化特征,揭示了表征其生长形态结构分式维数D的物理意义,同时考查了格子模型对簇合物生长形态的影响以及自调整模型的动力学行为。     

Theory and simulation of anisotropic pair correlations in ferrofluids in magnetic fields

Anisotropic pair correlations in ferrofluids exposed to magnetic fields are studied using a combination of statistical-mechanical theory and computer simulations. A simple dipolar hard-sphere model of the magnetic colloidal particles is studied in detail. A virial-expansion theory is constructed for the pair distribution function (PDF) which depends not only on the length of the pair separation vector, but also on its orientation with respect to the field. A detailed comparison is made between the theoretical predictions and accurate simulation data, and it is found that the theory works well for realistic values of the dipolar coupling constant (λ = 1), volume fraction (φ ≤ 0.1), and magnetic field strength. The structure factor is computed for wavevectors either parallel or perpendicular to the field. The comparison between theory and simulation is generally very good with realistic ferrofluid parameters. For both the PDF and the structure factor, there are some deviations between theory and simulation at uncommonly high dipolar coupling constants, and with very strong magnetic fields. In particular, the theory is less successful at predicting the behavior of the structure factors at very low wavevectors, and perpendicular Gaussian density fluctuations arising from strongly correlated pairs of magnetic particles. Overall, though, the theory provides reliable predictions for the nature and degree of pair correlations in ferrofluids in magnetic fields, and hence should be of use in the design of functional magnetic materials.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Field induced rotational viscosity of ferrofluid: effect of capillary size and magnetic field direction

In the present investigation we report the effect of capillary diameter and the direction of applied magnetic field on the rotational viscosity of water and kerosene based ferrofluids. We found that changes in the field induced rotational viscosity are larger in the case of water based magnetic fluid than that of kerosene based fluid. The field induced rotational viscosity is found to be inversely proportional to the capillary diameter and it falls exponentially as a function of the angle between the direction of field and vorticity of flow. Magnetophoretic mobility and hydrodynamic volume fraction of nanomagnetic particles are determined for above cases.     

Comparative analysis of the structure of sterically stabilized ferrofluids on polar carriers by small-angle neutron scattering

Results of experiments on small-angle neutron scattering from ferrofluids on polar carriers (pentanol, water, methyl-ethyl-ketone), with double-layer sterical stabilization of magnetic nanoparticles, are reported. Several types of spatial structural organization are observed. The structure of highly stable pentanol-based samples is similar to that of stable ferrofluids based on organic non-polar carriers (e.g., benzene) with mono-layer covered magnetic nanoparticles. At the same time, the effect of the interparticle interaction on the scattering is stronger in polar ferrofluids because of the structural difference in the surfactant shell. The structure of the studied methyl-ethyl-ketone- and water-based ferrofluids essentially different from the previous case. The formation of large (>100 nm in size) elongated or fractal aggregates, respectively, is detected even in the absence of external magnetic field, which corresponds to weaker stability of these types of ferrofluids. The structure of the fractal aggregates in water-based ferrofluids does not depend on the particle concentration, but it is sensitive to temperature. A temperature increase results in a decrease in their fractal dimension reflecting destruction of the aggregates. In addition, in water-based ferrofluids these aggregates consist of small (radius approximately 10 nm) and temperature-stable primary aggregates.     

PREPARATION AND CHARACTERIZATION OF PVA COATED MAGNETIC NANOPARTICLES*

Polyvinyl alcohol coated magnetic particles (PVA ferrofluids) have been synthesized by chemical co-precipitationof Fe(Ⅱ)/Fe(Ⅲ) salts in 1.5 mol/L NH_4OH solution at 70℃ in the presence of PVA. The resultant colloidal particles havecore-shell structures, in which the iron oxide crystallites form the cores and PVA chains form the shells. The hydrodynamicdiameter of the colloidal particles is in the range of 108 to 155 nm, which increases with increasing PVA concentration from5 wt% to 20 wt%. The size of the magnetic cores is ca. 5～10 nm, which is relatively independent of PVA concentration.Under transmission electron microscopic (TEM) examination, the magnetic cores exhibit somewhat irregular shapes varyingfrom spherical, oval, to cubic. Magnetometry measurement revealed that the PVA coated magnetic particles aresuperparamagnetic. The saturation magnetization of 5 wt% and 20 wt% PVA ferrofluids at 300 K is 54 and 49 emu/g.respectively. All the PVA ferrofluids exhibited excellent colloidal stability in pure water and phosphate buffer saline (PBS,pH=7.4). The ferrofluids can remain stable in above solutions for more than three months at 4℃.     

水基自形成CoFe2O4 磁性液体的零磁场粘滞特性

The plot of viscosity versus particle volume fraction for the water carrier of self-formed CoFe2O4 magnetic fluid is abnormal in zero magnetic field. However,the viscosity theory of the suspension with the global rigid particle filling cannot explain the experiment well. That is because the nanoparticles have aggregated before preparation of magnetic fluid. The fact is found that the sedimentation without magnetic field and the becoming chains in magnetic field of this type of magnetic fluid need the big particles which core are pre-aggregates by researching the interaction of particles of magnetic fluid. Around the big particles,nanoparticles are absorbed with the type of dynamic state. It is on that idea that the model of fluctuant aggregation is made. So,the average diameter,Einstein ratio and particles size distributive deviation of free suspended bodies in zero magnetic fluid are the functions of the particles volume fraction. And then,Popplewell’s formula of the viscosity is modified with this model. As a result,a well-fitted curve is obtained.     

Experimental characterization and viscoelastic modeling of isotropic and anisotropic magnetorheological elastomers

The paper presents experimental research and numerical modeling of dynamic properties of magnetorheological elastomers (MREs). Isotropic and anisotropic MREs have been prepared based on silicone matrix filled by micro-sized carbonyl iron particles. Dynamic properties of the isotropic and anisotropic MREs were determined using double-lap shear test under harmonic loading in the displacement control mode. Effects of excitation frequency, strain amplitude, and magnetic field intensity on the dynamic properties of the MREs were examined. Dynamic moduli of the MREs decreased with increasing the strain amplitude of applied harmonic load. The dynamic moduli and damping properties of the MREs increased with increasing the frequency and magnetic flux density. The anisotropic MREs showed higher dynamic moduli and magnetorheological (MR) effect than those of the isotropic ones. The MR effect of the MREs increased with the rise of the magnetic flux density. The dependence of dynamic moduli and loss factor on the frequency and magnetic flux density was numerically studied using four-parameter fractional derivative viscoelastic model. The model was fitted well to experimental data for both isotropic and anisotropic MREs. The fitting of dynamic moduli and loss factor for the isotropic and anisotropic MREs is in good agreement with experimental results.     

Ferrofluids Containing Fe3O4 Nanoparticles in Solidified Photoresist Carrier

Ferrofluids, formed by magnetic nanoparticles uniformly dispersed in a liquid carrier, respond to an external magnetic field, which enable the fluid's position by applying a magnetic field. Here, ferrofluids composed of Fe₃O₄ nanoparticles with oleic acid and oleylamine as the surfactant and photoresist, respectively, were prepared. Under an external magnetic field, the movement and the position of ferrofluids and the injection of the fluids into complex shapes were easily achieved. The ferrofluid surfaces were distorted under the magnetic field, and the surface structue was controlled by the applied field strength. Using a photoresist as the liquid carrier, it was possible to solidify the ferrofluids by UV irradiation. The shape and the position of the solid superparamagnetic nanoparticles/polymer composites were also determined by the external magnetic field.