F. González-Caballero

Measurement and interpretation of electrokinetic phenomena - (IUPAC technical report)

In this report, the status quo and recent progress in electrokinetics are reviewed. Practical rules are recommended for performing electrokinetic measurements and interpreting their results in terms of well-defined quantities, the most familiar being the z-potential or electrokinetic potential. This potential is a property of charged interfaces, and it should be independent of the technique used for its determination. However, often the z-potential is not the only property electrokinetically characterizing the electrical state of the interfacial region; the excess conductivity of the stagnant layer is an additional parameter. The requirement to obtain the z-potential is that electrokinetic theories be correctly used and applied within their range of validity. Basic theories and their application ranges are discussed. A thorough description of the main electrokinetic methods is given; special attention is paid to their ranges of applicability as well as to the validity of the underlying theoretical models. Electrokinetic consistency tests are proposed in order to assess the validity of the z-potentials obtained. The recommendations given in the report apply mainly to smooth and homogeneous solid particles and plugs in aqueous systems; some attention is paid to nonaqueous media and less ideal surfaces.

Rheological study of the stabilization of magnetizable colloidal suspensions by addition of silica nanoparticles

An experimental investigation is described on the stability of magnetorheological fluids (MRFs) consisting of iron suspensions in silicone oil with a thixotropic agent (silica nanoparticles) as stabilizer. The rheological properties were investigated using a commercial rheometer with a parallel-plate measuring cell. Several kinds of experiments were performed in steady-state, oscillatory, and transient regimes. The effects of the volume fraction of magnetic particles, the concentration of silica, magnetic flux density, B, and waiting time after preshear on the rheology of the MRFs were considered. Steady-state measurements demonstrated that our systems only display plastic behavior, for which a yield stress, σy, is appreciable, for the highest iron concentrations and/or magnetic fields. The yield stress was found to be independent of the magnetic flux density when the concentration of silica particles was large enough (> ∼20 g/L). This is a manifestation of the entrapment of iron particles in the silica g...

Sedimentation and redispersion phenomena in iron-based magnetorheological fluids

In this work, the effect of three different additives (oleic acid, aluminum stearate, and silica nanoparticles) on the aggregation, sedimentation, and redispersibility of concentrated iron-based magnetorheological fluids was investigated. With this aim, the sedimentation behavior was analyzed using an electromagnetic induction method, which is suitable for studying the sedimentation of opaque magnetic suspensions. The redispersibility was studied, in a quantitative way, by means of rheological measurements, both in the presence and in the absence of external magnetic field. For this purpose, samples were subjected to a constant shear stress at different moments (steps) of the settling process. The time evolution of the corresponding shear rate was measured at each step. Interestingly, it was found that although the addition of oleic acid or aluminum stearate does not avoid particle settling, the redispersibility of the suspensions is considerably enhanced. On the contrary, silica nanoparticles behave as a...

Preparation of stable magnetorheological fluids based on extremely bimodal iron–magnetite suspensions

The high magneto-viscous response of magnetorheological fluids (MRFs) comes from the large size (≈1 μm) of the magnetic particles dispersed in the carrier liquid. Unfortunately, in the absence of a magnetic field, this large size constitutes the origin of some problems facing the technological applications of MRFs. These problems are (i) the instability of the suspensions caused by the fast settling of the high density magnetic particles used, and (ii) the poor redispersibility due to an irreversible aggregation. In this work, we used an electromagnetic induction method to study the stability of MRFs containing micron-sized iron particles dispersed in ferrofluids composed by oleate-covered magnetite nanoparticles dispersed in kerosene. Interestingly, we demonstrated that the sedimentation rate in iron/ferrofluid suspensions can be significantly lower than in iron/kerosene MRFs.

Magnetorheology for suspensions of solid particles dispersed in ferrofluids

In this work, the magnetorheological properties of suspensions of micron-sized iron particles dispersed in magnetite ferrofluids were studied. With this aim, the flow properties of the suspensions in the steady-state regime were investigated using a commercial magnetorheometer with a parallel-plate measuring cell. The effect of both magnetite and iron concentration on the magnitude of the yield stress was studied for a broad range of magnetic fields. In addition, the experimental values of the yield stress were compared with the predictions from the chain model. With this purpose the values of the yield stress were obtained by means of finite element calculations. Interestingly, it was found that the experimental yield stress increases with the concentration of magnetite nanoparticles in the ferrofluid. Unfortunately, this behaviour is not obtained from calculations based on the chain model, which predict just the opposite trend.

Dynamic characterization of extremely bidisperse magnetorheological fluids

In this work, we investigate the stability and redispersibility of magnetorheological fluids (MRFs). These are disperse systems where the solid is constituted by ferro- or ferri-magnetic microparticles. Upon the application of external magnetic field, they experience rapid and reversible increases in yield stress and viscosity. The problem considered here is first of all the determination of their stability against sedimentation, an essential issue in their practical application. Although this problem is typically faced through the addition of thixotropic agents to the liquid medium, in this work, we propose the investigation of the effect of magnetic nanoparticles addition, so that the dispersion medium is in reality a ferrofluid. It is found that a volume fraction of nanoparticles not higher than 3% is enough to provide a long-lasting stabilization to MRFs containing above 30% iron microparticles. In the, in fact unavoidable, event of settling, the important point is the ease of redispersion of the sediment. This is indirectly evaluated in the present investigation by measuring the penetration force in the suspension, using a standard hardness needle. Again, it is found that the nanoparticles addition produces soft sediments by avoiding short-range attractions between the large iron particles. Finally, the performance of the designed MRFs is evaluated by obtaining their steady-state rheograms for different volume fractions of magnetite and different magnetic field strengths. The yield stress is found to be strongly field-dependent, and it can achieve the high values expected in standard magnetorheological fluids but with improved stability and redispersibility.

Intensification of electrodialysis by applying a non-stationary electric field

Electrodialysis is an effective method of water desalination. However, the efficiency of the method is limited by the concentration polarization of the ion-exchange membranes. Applying an electric field with special pulse characteristics can diminish the effect of the concentration polarization. A theoretical analysis is carried out for galvanostatic and potentiostatic pulse regimes. The time dependencies of the extent of the concentration polarization near the membrane surface during the pulse are described theoretically for both pulse regimes and a qualitative discussion of the pause duration is presented. The main characteristic of the non-stationary process is the transition time between the state without polarization and the state with stationary polarization. In principle, the electrodialysis process can be intensified significantly when the applied pulse is sufficiently smaller than this transition time. Experimental results are quoted that qualitatively support the model predictions. It is shown that the desalination can be intensified several times, depending on the pulse-pause characteristics.

Preparation and characterization of iron-based magnetorheological fluids stabilized by addition of organoclay particles.

Suspensions of micrometer-sized iron particles (10 vol %) dispersed in kerosene and stabilized by addition of organoclay particles were prepared. The magnetization curves of these suspensions were measured, and their sedimentation and redispersion behaviors were analyzed as a function of clay concentration by means of optical and rheological methods. Furthermore, their magnetorheological properties were investigated using a controlled rate magnetorheometer and the effect of clay concentration on these properties was also analyzed. These experiments showed that the addition of clay slows down iron particle settling and eases the redispersion of the iron-based suspensions without masking their magnetorheological properties. Two mechanisms were found to be involved in this behavior: (i) the formation of a clay gel network and (ii) the presence of heterogeneous iron-clay adhesion.

Normal force study in concentrated carbonyl iron magnetorheological suspensions

The yield behavior of concentrated carbonyl iron magnetorheological fluids (MRF) is investigated measuring the normal force during shear flow in a plate–plate controlled-stress rheometer. For high enough external magnetic fields, a positive normal force is obtained below the yield point. This result is not explained using affine deformation chain models. However, the assumption of gapspanning particle chains and spheroidal aggregates of spheres predicts not only a positive normal force but also a maximum if we plot the normal force as a function of the strain, a result also found experimentally. The field dependence of the normal force suggests the existence of a threshold field, likely associated to the formation of gapspanning structures in the MRF. Another possible explanation for the maximum in the normal force lies on the phase transition from homogeneous to layered structures with cylindrical symmetry in the suspension. Steady-state and oscillometry studies show that the maximum in the normal force ...

The effect of the concentration of dispersed particles on the mechanisms of low-frequency dielectric dispersion (LFDD) in colloidal suspensions

Abstract There are two mechanisms which are currently used to explain the low-frequency (kHz range) dispersion of the dielectric permittivity of suspensions in electrolyte solutions (LFDD). The first, the surface diffusion mechanism (SDM), associates the LFDD with the diffusion of bound ions along the particle surface caused by the applied electric field. The second, the volume diffusion mechanism (VDM), follows from the generalization for alternating fields of the classical theory of the relaxation effect in electrophoresis and associates the LFDD with the diffusion of free ions in the diffuse double layer. It has been found that VDM is much more strongly dependent on particle concentration than SDM, opening new possibilities for the investigation of each of these two mechanisms separately. The reason is that when the concentration of particles in suspension increases, the characteristic length for the propagation of volume diffusion processes decreases together with the decrease of the free electrolyte volume, whereas the characteristic length for the surface diffusion remains constant. Correspondingly, when particle concentration is raised, the relaxation time of the VDM effect must decrease, whereas it must remain constant for the SDM mechanism. Thus, by varying the concentration of particles in suspension, one can separate the dispersion curves of SDM and VDM. A simple model is elaborated which can be useful to predict the volume fraction dependence of the parameters of LFDD; in particular, its amplitude and critical frequency. The results are compared with experimental data obtained with polymer latex dispersions of volume fractions ranging from 3 to 16%. It is found that the dielectric behaviour (the volume fraction dependence of both the amplitude and critical frequency of LFDD) of the dispersions is reasonably well explained with our model, thus demonstrating that VDM prevails in the systems studied. Experimental data previously found by other authors are also discussed in the light of the model presented.