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.     

Structure changes of electrorheological fluids based on polyaniline particles with various hydrophilicities and time dependence of shear stress and conductivity during flow

Particles of polyaniline protonated with perfluorooctanesulfonic acid provided a material with hydrophobic surface. This property enabled its perfect dispersion in silicone oil due to its good compatibility with the hydrophobic medium. In contrast, in a suspension of hydrophilic polyaniline particles doped with sulfamic acid, strong interactions of particles prevailed, which led to the formation of entangled chains of aggregated particles in suspension. The difference in structural properties of suspensions exists already in the absence of electric field and significantly influences their electrorheological behavior after application of electric field. The formation of electrorheological structure has been monitored by recording time dependences of the shear stress and the electric current passing through the flowing suspensions.     

Water-activated cellulose-based electrorheological fluids

The performance of electrorheological (ER) fluids containing cellulose particles dispersed in lubricating oil was investigated as a function of particle water content, DC electric field strength, particle concentration, and temperature. Over a range of applied electric fields (0–3 kV/mm), yield stress was observed to increase with increasing cellulose moisture content up to 8.5 wt% followed by a decrease. Water adsorbed by cellulose particles used in these systems was shown to be non-freezing bound water. The maximum ER response for a cellulose-based fluid at 25 °C was observed at a moisture content near the transition of less mobile liquid-like (LM) water to more mobile liquid-like (MM) non-freezing water. At a constant moisture level, yield stress increased linearly with increases in either electrical field strength or particle concentration, while the ER effect decreased with increasing temperature. The present study concludes that the performance of water-activated ER fluids based on cellulose particles is influenced strongly by the mobility of non-freezing bound water adsorbed onto cellulose.     

Field-induced structural ordering in electrorheological fluids

Structural relaxations of an electrorheological fluid (ERF) due to changes in the applied electrical field strength or shear rate are observed on time scales 1 s<t<40 000 s. Commercial ERFs consisting of mesoscopic polyurethane particles in a silicone oil matrix were studied by three different experimental techniques in order to obtain and compare the characteristic relaxation times. It is demonstrated that dielectric spectroscopy, viscosimetry and light transmission experiments represent the same results concerning the structural relaxation phenomena of ERFs when electrical fields are applied. The tendency of strong induced dipoles to align the particles in the direction of the field increases the effective dipole moment and therefore , the shear viscosity and the amount of light transmitted along the field direction in an ITO/glass sandwich cell. The optical experiment is capable of resolving fast processes within the first 1 ms if large electrical fields are applied. The effects of electrophoresis and shearing, which both counteract the field induced structures, are also addressed.     

The dielectric properties and flow of electrorheological fluids based on polymer-coated nanodispersed barium tetraacetate titanyl particles upon a dynamic shear in electric fields

The shear stress in flowing electrorheological fluids consisting of PMS-20 poly(dimethylsiloxane) filled with nanodispersed barium tetraacetate titanyl particles coated with polymers (polyethyleneimine, poly(ethylene glycol), and polyethyloxazoline) has been studied as depending on the strengths of direct- and alternating-current (f = 50 Hz) electric fields. Results of analyzing the dielectric spectra of electrorheological fluids in a frequency range of 25–10⁶ Hz have been presented. The values of the shear stress in the flowing fluids as depending on the nature of a polymer adsorbed on the particle surface decrease in a series corresponding to a reduction in the Maxwell–Wagner relaxation times of the suspensions. The current-voltage characteristics of the electrorheological fluids at high voltages (up to 5 kV) indicate the realization of the mechanism of currents limited by the space charge. The influence of an adsorbed polymer on the magnitude of the electrorheological effect is reduced to blocking polar groups on the particle surface and variations in the conductivity, effective dielectric permittivity, and loss tangents of filler materials. An increase in the contribution from these factors leads to a gradual decrease in the magnitude of the electrorheological effect.     

Dynamic polarizability of rotating particles in electrorheological fluids

A rotating particle in electrorheological (ER) fluid leads to a displacement of its polarization charges on the surface which relax toward the external applied field E0, resulting in a steady-state polarization at an angle with respect to E0. This dynamic effect has shown to affect the ER fluid properties dramatically. In this paper, we develop a dynamic effective medium theory (EMT) for a system containing rotating particles of finite volume fraction. This is a generalization of established EMT to account for the interactions between many rotating particles. While the theory is valid for three dimensions, the results in a special two-dimensional configuration show that the system exhibits an off-diagonal polarization response in addition to a diagonal polarization response, which resembles the classic Hall effect. The diagonal response monotonically decreases with increasing rotational speed, whereas the off-diagonal response exhibits a maximum at a reduced rotational angular velocity omega0, compared to the case of isolated rotating particles. This implies a way of measurement on the interacting relaxation time. The dependencies of the diagonal and off-diagonal responses on various factors, such as omega0, the volume fraction, and the dielectric contrast, are discussed.     

A new approach of enhancing the shear stress of electrorheological fluids of montmorillonite nanocomposite by emulsion intercalation of poly-N-methaniline

Poly-N-methaniline/montmorillonite (PNMA-MMT) nanocomposite particles with high dielectric constant as well as suitable conductivity were synthesized by an emulsion intercalation method and characterized by FT-IR, XRD, and TEM spectrometry, respectively. The electrorheological (ER) properties of the suspensions of PNMA-MMT particles in silicone oil (20 wt%) were investigated under DC electric fields. It was found that the shear stress of poly-N-methaniline/montmorillonite electrorheological fluid (ERF) is 6.0 kPa in 3 kV/mm (74.5 s(-1)), which is 3.6 times that of electrorheological fluid at zero field, and also much higher than that of pure poly-N-methaniline (PNMA) and montmorillonite (MMT). In the range of 10-90 degrees C, the shear stress changes slightly with the temperature. The sedimentation ratio of PNMA-MMT ERF was about 97% after 60 days. Furthermore, the dielectric constant of PNMA-MMT nanocomposite was increased 3.74 times that of PNMA and 1.99 times that of MMT at 1000 Hz, the dielectric loss tangent also increased about 1.58 times that of PNMA. It is apparent that the notable ER effect of PNMA-MMT ER fluid was attributed to the prominent dielectric property of the poly-N-methaniline/montmorillonite nanocomposite particles.     

Polarization processes in electrorheological fluids based on conductive polymers

Electrorheological (ER) fluids are composed of dielectric particles dispersed in an inert liquid of low electric permittivity. Upon the application of an electric field ER fluids rapidly solidify, or increase their viscosity. Characteristic increase of the viscosity of ER fluids is due to the formation of particle chains that bridge the electrodes. This process is greatly affected by polarization processes within the solid phase and at the surface of the grains. These phenomena are governed by dopants, functional groups, structure of the solid particles and the solid/liquid interface. To find relations between parameters of the ER effect and material properties of components of ER fluids, two main types of the materials were investigated: conjugated polymers [polyphenylene (PPP), pyrolyzed polyacrylonitrile (PAN) and polythiophene] and solid electrolytes based on polyacrylonitrile complexed with inorganic salts. It was found that the ER activity resulted from surface polarization processes due to the presence of polar species (PAN) or bulk polarization related to mobile ions (PPP). Polythiophene, despite the presence of a conjugated system of multiple bonds, showed only residual ER effect. Solid electrolyte‐based fluids exhibited relatively high activity originated from ionic polarization. Copyright © 2006 John Wiley & Sons, Ltd.     

New analysis of yield stress on giant electrorheological fluids

A new universal yield stress scaling equation is proposed to accurately model experimental data for giant electrorheological (GER) fluids. This new equation expressed in modified Bessel function predicts both regions of polarization effect predominant in the low electric field strength applied and polar molecule-dominating GER behavior, as well as collapses the experimental data of yield stress in a single line for a broad range of electric field strengths.     

Properties of electrorheological fluids based on nanocrystalline cerium dioxide

Effect of conditions of nanocrystalline cerium dioxide preparation from aqueous solutions on its composition and physicochemical properties and on dielectric characteristics of CeO₂ suspensions in polydimethylsiloxane PMS-20 and the magnitude of electrorheological effect for these suspensions has been analyzed. Relationship between physicochemical properties of CeO₂ nanopowders and polarization and functional characteristics of electrorheological fluids derived therefrom has been established.     

Rheodielectric spectroscopy on heterogeneous polymer systems —electrorheological fluids

The technique of rheodielectric spectroscopy is used to investigate the dielectric behaviour of electrorheological fluids (ERF) as a function of external electrical DC-field and/or shear rate. Commercial ERF's consisting of mesoscopic polyurethane particles in a silicone oil matrix were studied. The particles contain a salt which leads to strong dipole moments via the Maxwell-Wagner-Polarization (MWP) if subjected to an external electrical field. In an electrical field the dipoles and, concomittantly, the particles motion become correlated leading to the formation of solid-like structures and significant changes in the viscosity. We demonstrate that dielectric spectroscopy is capable of monitoring the field and shear rate effects in terms of relaxation strength and relaxation time of the MWP. In electrical or shear fields dipole-dipole correlations increase the MWP's relaxation strength, so that we are able to observe structure formation with dielectric spectroscopy, especially the time resolved response of the ERF to changes in the electrical field or the shear rate.     

Structure development under transient shear flow in semidilute polystyrene solution

The shear-induced concentration fluctuations or phase separation of a semidilute solution comprised of polystyrene (PS) as a solute and dioctylphthalate (DOP) as a solvent (PS/DOP) was investigated by using real-time and in-situ shear-small-angle light scattering and shear-phase-contrast optical microscopy. When a transient shear flow with a fixed shear rate γ greater than a critical value γ_C was imposed on the solution, a unique anisotropic scattering pattern was observed some time after onset of shear. This pattern was found to be identical to the “butterfly pattern” previously reported for the same solutions under steady shear flow with γ_C. When the shear flow was ceased before the scattered intensity reached a steady state, the scattered intensity rapidly increased toward a maximum intensity, and then decreased toward the intensity of the quiescent solution with time. From the phase-contrast microscopy, this immediate increment of the scattered intensity after the shear cessation was found to arise from the increment in amplitude of the concentration fluctuations along flow direction. The characteristic length scale of the fluctuations was about 2.5 μm in this experiment, almost independent of the shear rate imposed on the solution.     

Parallel superposition of small- and large-amplitude oscillations upon steady shear flow of polymer fluids

The parallel superposition of small- and large-amplitude oscillations upon steady shear flow of elastic fluids has been considered. Theoretical results, obtained by numerical methods, are based upon the Leonov viscoelastic constitutive equation. Steady-state components, amplitude, and phase angle of oscillatory components of the shear stress, the first and second normal-stress differences as a function of shear rate, deformation amplitude, and frequency have been calculated. These oscillatory components include the first harmonic of the shear stresses and the first and second harmonic of the normal stresses. In the case of small-amplitude superposition, the effect of the steady shear flow upon frequency-dependent storage and loss moduli has been determined and compared with experimental data available in the literature for polymeric solutions and melts. In the case of large-amplitude superposition, the effect of oscillations upon the steady shear flow characteristics has been determined and compared with our experimental data for a polymeric melt. The experimental results for shear stress components have been found to be in good agreement with theoretical predictions, although there are some deviations for storage modulus at high shear rates. The deviations seem to be dependent on material. Moreover, the theory is unable to describe experimental data available for the first harmonic of normal stresses.     

Yield stress analysis of 1D calcium and titanium precipitate-based giant electrorheological fluids

1D calcium and titanium composite nanorods synthesized were applied as electrorheological (ER) active materials with extremely high static yield stresses, i.e., giant ER effect. The yield stress of this giant ER fluid was analyzed using a new universal yield stress scaling equation in the form of the modified Bessel functions with two different limiting behaviors in a low and high electric field region. The universal yield stress equation collapsed the yield stress data onto a single curve.     

Structure development in confined polymer blends: steady-state shear flow and relaxation

In this work, the structure development in immiscible polymer blends in confined geometries is systematically investigated. Poly(dimethylsiloxane)/poly(isobutylene) blends with a droplet-matrix structure are subjected to simple shear flows. The confined environment is created by using a Linkam shearing cell in which the gap is systematically decreased to investigate the transition from "bulk" behavior toward "confined" behavior. Small-angle light scattering experiments in a confinement, which have not yet been reported in the literature, and also microscopy are used to observe the morphology development during steady-state shearing and relaxation. These experiments indicate that the size and relaxation of single droplets in a confined environment are still governed by the relations that describe the structure development in bulk situations. Yet, depending on the applied shear rates and blend concentrations, the droplets organize in superstructures such as pearl necklaces or extended superstrings in a single layer between the plates. These structures are stable under flow. To observe a single layer, a critical ratio of droplet size to gap spacing is required, but this ratio is clearly below the one already reported in the literature.     

Structure and dynamics of concentration fluctuations in a polymer blend solution under shear flow

The technique of small-angle light scattering (SALS) has been employed to investigate the time-dependent behavior of a single-phase, semidilute solution of polystyrene and polybutadiene in dioctyl phthalate under shear flow. Concentration fluctuations in the polymer blend solution are found to grow with time in the direction of flow, and their orientation angles evolve from 45° from the flow direction toward 0°, with the steady-state value being dependent on shear rate. SALS patterns are simulated using a modified Cahn-Hilliard-Cook model, with an additional collective restoring force to account for polymer elasticity. Predictions from this modified model for the orientation angles of the concentration fluctuations are in excellent agreement with the experimental results. Our model also predicts that the quiescent structure factor has a Gaussian form and that the steady-state orientation of the scattering patterns is dependent on shear rate. These predictions are also in good agreement with our experimental observations. © 1994 John Wiley & Sons, Inc.     

Proteins in a shear flow

The conformational dynamics of a single protein molecule in a shear flow is investigated using Brownian dynamics simulations. A structure-based coarse grained model of a protein is used. We consider two proteins, ubiquitin and integrin, and find that at moderate shear rates they unfold through a sequence of metastable states-a pattern which is distinct from a smooth unraveling found in homopolymers. Full unfolding occurs only at very large shear rates. Furthermore, the hydrodynamic interactions between the amino acids are shown to hinder the shear flow unfolding. The characteristics of the unfolding process depend on whether a protein is anchored or not, and if it is, on the choice of an anchoring point.     

Bidisperse electrorheological fluids using hydrolyzed styrene-acrylonitrile copolymer particles: synergistic effect of mixed particle size

Monodisperse micron-sized styrene-acrylonitrile copolymer (SAN) particles with three different sizes (about 5, 10, and 15 microm) were prepared by a two-step seeded polymerization and used for a study of bidisperse electrorheological (ER) suspensions. The effect of the particle size and the size-mixing fraction on ER properties was studied with varying the size of these monodisperse copolymer particles. When the two particle sizes were mixed, the suspension generally showed a decrease in the shear yield stress, reaching a minimum value. However, a bidisperse ER suspension of large particles containing a small fraction of fine particles showed an interesting synergy effect of size mixing on ER response, giving enhanced yield stresses over the other size-mixing fractions. This synergistic ER suspension also showed a great increase in the viscoelastic property. The current density of suspensions was maximum at the synergistic bidisperse suspension. This synergy effect in a particular bidisperse suspension was investigated in view of the structure model consideration and was concluded to be due to a close packing and a peculiar structural ordering at an optimum size ratio and mixing fraction.