Dispersion Stability and Electrorheological Properties of Polyaniline Particle Suspensions Stabilized by Poly(vinyl methyl ether)

In the present article, a novel method of stabilization of a semi conductive polyaniline particle nonaqueous suspension of electrorheological (ER) materials was introduced. Using as the steric stabilizer poly(vinyl methyl ether) (PVME), a dispersion polymerization of aniline was performed and stable aqueous dispersions of the polyaniline were obtained. However, a stable colloidal suspension of polyaniline in silicone oil medium can be obtained only with a low concentration of PVME (0.75%), although the average size of the individual, redispersed particles in oil generally decreased with increasing concentration of PVME. At higher concentrations of PVME, formation of highly packed particle aggregates was investigated, as seen in the scanning electron microscopy images. The polyaniline suspension stabilized by 0.75% PVME content exhibited the best dispersing state and, therefore, showed the highest zero-field viscosity. Such a well-stabilized polyaniline suspension also showed the maximum ER property, namely the largest normalized yield stress in an electric field. Copyright 2001 Academic Press.     

Synthesis and electrorheological characterization of emulsion-polymerized dodecylbenzenesulfonic acid doped polyaniline-based suspensions

The electrorheological (ER) properties of dodecylbenzenesulfonic acid (DBSA) doped polyaniline suspensions in silicone oil were investigated. In contrast to chemically polymerized polyaniline in an acidic aqueous medium by oxidation polymerization, we adopted an emulsion polymerization technique in which aniline is polymerized in an emulsion of water and a nonpolar (or weakly polar) organic solvent. The effects of electric field strength and particle concentration on the ER properties of DBSA-doped polyaniline suspensions in silicone oil were then examined. Rheological measurements were also carried out using a rotational rheometer with a high-voltage generator in both controlled shear rate and shear stress modes, and the results showed that the ER properties were enhanced by increasing the particle concentration and electric field. Received: 23 August 1999 Accepted: 6 April 2000     

Improved electrorheological effect in polyaniline nanocomposite suspensions

We prepared polyaniline (PANI)/clay composites that are composed of both PANI-clay nanocomposite particles and pure PANI particles. The PANI-clay nanocomposite particles were made during the polymerization process, wherein PANI particles are attached on the surface of exfoliated clay particles modified by an aminosilane group. The PANI/clay composites were used as electrorheological fluids (ERFs) by dispersing them in silicon oil. The PANI-clay nanocomposite particles, which can form columnar structure under an electric field, strongly enhance the mechanical rigidity of the suspensions. The maximum yield stress of the PANI/clay composite suspensions (15 wt% in silicon oil) was 1.6 kPa at 3 kV/mm, while that of pure PANI was 300 Pa at the same electric field. A mechanism to explain the yield behaviors of the PANI-based nanocomposite suspensions is proposed.     

Monodisperse conducting colloidal dipoles with symmetric dimer structure for enhancing electrorheology properties

This study introduces an electrorheological (ER) approach that allows us to obtain remarkably enhanced ER properties by using monodisperse colloidal dimer particles. Two sets of colloidal particles, which are spheres and symmetric dimers, were synthesized employing the seeded polymerization technique. The aspect ratio of dimer particles was ~1.43. Then, the surface of the particles was coated with polyaniline by using the chemically oxidative polymerization method. After preparation of the particle suspensions having the same particle volume and concentration, their ER behavior was investigated with changing the electric field strength. At the same experimental condition, both shear stress and shear yield stress of the dimer particle suspension remarkably increased, compared with those of the spherical particle suspension. This attributes to the fact that the shape anisotropy of suspending particles effectively led to increase in the dipole moment under the electric field, thus resulting in formation of a well-structured colloidal chains between the electrodes.     

Electrorheological fluid characterization via a vertical oscillation rheometer

A custom designed vertical oscillation rheometer (VOR) is used for the rheological measurements of electrorheological (ER) fluids consisting of 15 and 20 vol.% semiconducting polyaniline particles suspended in silicone oil. The viscoelastic material functions, including complex viscosity and complex shear modulus, are measured via geometric parameters, measured force, and applied strain of the VOR. Viscoelastic properties of the ER fluids are also measured as a function of applied electric field strength and particle concentration. The VOR, equipped with a high voltage generator, can easily be constructed and used to measure ER properties. It is further found that polyaniline suspensions behave as viscoelastic materials in an electric field. In linear viscoelastic conditions, elasticity was promoted with the increment of electric field due to particle chain structure in the presence of the applied electric field. It is also found that the applied electric field rather than particle concentration enhanced the elasticity of ER fluids.     

Effect of Electrode Pattern on the Column Structure and Yield Stress of Electrorheological Fluids

For electrorheological (ER) suspensions, the aggregate structures of particles were observed in electric fields by the use of transparent cells with different electrode patterns. Although the suspension is dispersed to noninteracting particles without electric fields, many aggregates are formed on the electrode surface in electric fields. Since the dipole–dipole interactions cause chain structures of particles and equilibrium conformations of chains are always aligned with electric field, the aggregates indicate the presence of columns spanning the electrode gap. The particle concentration in columns which are developed between parallel-plate electrodes is about 22 vol %. In striped electrodes, the particles construct striped aggregates along the electrodes and no particles remain in the insulating region. The particle concentration in striped aggregates is about 35 vol %. The nonuniformity of electric field is responsible for the high particle concentration. The increase in particle concentration of column lead to the high yield stress of electrified suspension. Therefore, the ER performance of suspension as an overall response can be improved by the electrode design.     

Conductivity of flowing polyaniline suspensions in electric field

The formation of chain structures by polarized polyaniline (PANI) particles suspended in silicone oil in the electric field has been monitored by recording suspension conductivity in the course of time. For that purpose, three types of PANI particles differing in the conductivity (3.1 × 10⁻³, 1.7 × 10⁻¹, and 2.0 × 10⁻¹ S cm⁻¹) have been chosen out of a series of nine samples prepared by controlled protonation of PANI base in orthophosphoric acid solutions. Relaxation times reflecting this process and characterizing the rate of the response to the electric field decreased with particle conductivity, indicating a higher polarizability of particles. At the same time, the maximum conductivity of suspension increased as a consequence of the electric and shear forces acting on the particles. In the shear fields, shorter relaxation times appeared than at rest. The simultaneous measurement of the shear stress confirmed that the conductivity investigation can reliably characterize the development of electrorheological structures.     

Electrorheological properties and microstructure of silica suspensions

We present experimental and theoretical results on the electrorheological response and microstructure of colloidal suspensions composed of silica nanoparticles dispersed in a silicon oil, as a function of electric field strength and silica water content. Using small-angle neutrons scattering experiments, we determined the evolution of the static structure factor of the suspensions when an electric field is applied. Experimental data were fitted with model calculations using the Percus-Yevick solution for Baxter's hard-sphere adhesive potential. The obtained stickiness parameter is directly related to the polarization interactions that depend on the water content of silica particles. The influence of the polarization interparticle potential on the rheology of the silica dispersions was investigated in a second time. A microscopic theory for the shear viscosity of adhesive hard-sphere suspensions was successfully used which describes the steady shear viscosity of suspension in terms of the fractal concept.     

Electrorheology of aniline oligomers

Aniline oligomers were prepared by the oxidation of aniline with p-benzoquinone in aqueous solutions of methanesulfonic acid (MSA) of various concentrations. Their molecular structures were assessed by Fourier transform infrared spectroscopy. The electrorheological (ER) behavior of their silicone oil suspensions under applied electric field has been investigated. Shear stress at a low shear rate, τ _0.9, was used as a criterion of the rigidity of internal structures created by the application of an electric field. It was established from the fitting of the dielectric spectra of the suspensions with the Havriliak–Negami model that dielectric relaxation strength, as a degree of polarization induced by an external field contributing to the enhanced ER effect, increases and relaxation time, i.e., the response of the particle to the application of the field, decreases when a higher molar concentration of MSA is used. The best values were observed for suspensions of the sample prepared in the presence of 0.5 M of MSA. This suspension creates stiff internal structures under an applied electric field strength of 2 kV mm^?1 with τ _0.9 of nearly 50 Pa, which is even slightly of higher value than that obtained for standard polyaniline base ER suspension measured at the same conditions. The concentration of the MSA used in the preparation of oligomers seems to be a crucial factor influencing the conductivity, dielectric properties and, consequently, rheological behavior, and finally ER activity of their suspensions.     

Electrorheological fluids as colloidal suspensions

An increase in suspension stress transfer by many orders of magnitude upon application of an external electric field is commonly referred to as the electrorheological response. Suspensions displaying this behavior are often composed of a nonaqueous dispersion of colloidal particles. In this review, the current understanding of the origin of electrorheology is described in the context of a fundamental discussion of the colloidal forces relevant to these suspensions. We show that many of the observed phenomena can be described in terms of colloidal and electric field induced interparticle interactions. The field induced arrangement of a suspension, where columns of particles are formed along field lines, is intimately related to its rheological response. A review of particle interaction potential energies of both colloidal and electric origin provides basic scaling relationshios useful in understanding structural alterations and leads naturally to a discussion of models of a suspension's rheological response. Poorly understood areas such as the effect of charge carriers in the continuous phase and particle size, shape and chemistry are delineated to indicate areas deserving further research.     

Electrorheological behavior of suspensions of a substituted polyaniline with long alkyl pendants

The electrorheological (ER) properties of poly(2-dodecyloxyaniline) (PDOA) suspensions in silicone oil were investigated. The ER behavior of such suspensions of polyaniline particles depends on the type of stabilizer and doping or dedoping level. Here we report on the ER behavior of particles of a substituted polyaniline with long alkyl pendants. Rheological measurements were carried out using a rotational rheometer with high-voltage generator in both constant shear stress and rate modes. Suspensions of the as-synthesized polyaniline particles in silicone oil showed a substantial ER response.     

Electrorheological characterization of polyaniline-coated poly(methyl methacrylate) suspensions

Surface-conductive particles consisting of a poly(methyl methacrylate) (PMMA) core and a polyaniline (PA)-coated shell were synthesized and adopted as suspended particles for electrorheological (ER) fluids. The PA-PMMA composite particles synthesized were monodisperse and spherical in shape. The PA-PMMA suspensions in silicone oil showed typical ER characteristics under an applied electric field. The PA-PMMA composite particles possess a higher dielectric constant and conductivity than the pure PA particle, within an acceptable conductivity range for ER fluids, but the PA-based ER fluid showed larger shear-stress enhancement than the PA-PMMA-based systems. This phenomena can be explained by the interfacial polarizability of PA-based ER fluids, which is the difference between the ER fluid's dielectric constant and loss factor - this polarizability was higher than that of PA-PMMA-based ER fluids, as shown by the dielectric spectrum of each fluid. The insulating PMMA core suppressed the interfacial polarization in ER fluids, resulting in reduced interaction among particles under an imposed electric field.     

Electrorheological properties of hydrolyzed poly(glycidyl methacrylate) suspensions

 Electrorheological behavior of silicone oil suspensions of macroporous poly[(glycidyl methacrylate)-co-(ethylene dimethacrylate)]) (0.60 : 0.40 w) hydrolyzed to various degrees was investigated. Polarizability of particles expressed by the particle dipole coefficient and, consequently, pseudoplasticity of the system at low shear rates after application of an external electric field steeply increased with the hydrolysis degree of the copolymer. As the size and shape of particles remain unchanged during hydrolysis, a series of model suspensions with the same hydrodynamic properties (Newtonian or slightly pseudoplastic when no electric field was applied) but with different intensity of the electrorheological effect could be prepared. Under these conditions, the use of Mason number failed to correlate the apparent viscosity of suspensions of particles with different polarizability in the electric field. On the other hand, when polarizability of particles of a suspension system changes due to a higher temperature, a single curve in the plot of apparent viscosity vs. the Mason number could be obtained. Received: 17 February 1998 Accepted: 8 May 1998     

聚苯胺类电流变体的稳态剪切流动分析

对聚苯胺、及聚苯胺/聚丙烯酸盐复合粒子的稳态剪切流动行为进行了综合考察.结果表明, 在交流电场下,电流变体的剪切应力和剪切速率的关系符合Bingham流体形为.并对此现象进行了分析,提出用非理想塑性体的新模型来描述交流电场下聚苯胺类电流变体的稳态剪切流动.     

Electrorheological properties of suspensions of hollow globular titanium oxide/polypyrrole particles

Hollow globular clusters of titanium oxide (TiO₂) nanoparticles were synthesized by a simple hydrothermal method. The prepared particles were consequently coated by in situ polymerization of conductive polymer polypyrrole (PPy) to obtain novel core–shell structured particles as a dispersed phase in electrorheological (ER) suspensions. The X-ray diffraction analysis and scanning electron microscopy provided information on particle composition and morphology. It appeared that PPy coating improved the compatibility of dispersed particles with silicone oil which results in higher sedimentation stability compared to that of mere TiO₂ particles-based ER suspension. The ER properties were investigated under both steady and oscillatory shears. It was found that TiO₂/PPy particles-based suspension showed higher ER activity than that of mere TiO₂ hollow globular clusters. These observations were elucidated well in view of their dielectric spectra analysis; a larger dielectric loss enhancement and faster interfacial polarization were responsible for a higher ER activity of core–shell structured TiO₂/PPy-based suspensions. Investigation of changes in ER properties of prepared suspensions as a function of particles concentration, viscosity of silicone oil used as a suspension medium, and electric field strength applied was also performed.     

A Surfactant Bridge Model for the Nonlinear Electrorheological Effects of Surfactant-Activated ER Suspensions

In surfactant-activated electrorheological (ER) suspensions it is observed that the ER response shows linear ER behavior (F~E(2)) at small surfactant concentrations and nonlinear ER behavior (F~E(n), n approximately 1) at large surfactant concentrations. Here, a surfactant bridge model is developed to explain the nonlinear ER behavior of surfactant-activated ER suspensions. The model shows that the formation and size of a surfactant bridge depend on various variables, especially the electric field strength, the surfactant surface tension, and the initially adsorbed amount of surfactants on particles. The predicted dependence of the formation and size of a surfactant bridge on the electric field strength and the initially adsorbed amount of surfactants is consistent with the observations. Also, the model indicates that there is a critical minimum electric field E(crit) for the formation of a surfactant bridge, and the estimated E(crit) shows good agreement with the observations. The force acting between particles is composed of the electrostatic force and force associated with surface tension. However, it is found that the contribution of the force associated with surface tension can be ignored and the electrostatic force is dominant regardless of the formation of surfactant bridges between particles. When surfactant bridges are formed between particles, the predicted force shows nonlinear ER behavior (F~E(n), n approximately 1), consistent with the observed nonlinear ER behavior at large surfactant concentrations. When no surfactant bridge is formed, the predicted force is proportional to the electric field squared (F~E(2)), consistent with the interfacial polarization. The model can successfully predict the nonlinear ER behavior at large surfactant concentrations, confirming that the nonlinear ER behavior of surfactant-activated ER suspensions arises from the observed formation of surfactant bridges between particles. Copyright 2001 Academic Press.     

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.     

An investigation of electrorheological properties of calcium carbonate suspensions in silicone oil

In this study, electrorheological behavior of suspensions prepared from 0.9 and 5.0 µm calcium carbonate particulates, dispersed in insulating silicone oil medium was investigated. Sedimentation stabilities of suspensions (c = 5 wt %) prepared using these calcium carbonate powders were determined to be 6 and 4 days, respectively. Electrorheological activity of all the suspensions was observed to increase with increasing electric field strength, concentration and decreasing shear rate. Shear stress of calcium carbonate suspensions increased linearly with increasing concentrations of the particles and with the applied electric field strength. Electric field viscosity of all the suspensions was decreased sharply with increasing shear rate and particle size, showing a typical shear thinning non-Newtonian visco-elastic behavior. Effects of elevated temperature and polar promoter onto electrorheological activity of calcium carbonate/silicone oil system were also investigated.__________From Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 268–273.Original English Text Copyright © 2005 by Yilmaz, Ünal, Yavuz.This article was submitted by the authors in English.     

ELECTRORHEOLOGICAL PROPERTIES OF POLYANILINE/PUMICE COMPOSITE SUSPENSIONS

Electrorheological （ER） properties of polyaniline （PAni）, pumice and polyaniline/pumice composites （PAPC） were investigated. Polyaniline and PAni/pumice composite were prepared by oxidative polymerization. PAni/pumice particlesbased ER suspensions were prepared in silicone oil （SO）, and their ER behavior was investigated as a function of shear rate, electric field strength, concentration and temperature. Sedimentation stabilities of suspensions were determined. It has been found that ER activity of all the suspensions increases with increasing electric field strength, concentration and decreasing shear rate. It has shown that the suspensions have a typical shear thinning non-Newtonian viscoelastic behavior. Yield stress of composite suspensions increased linearly with increasing applied electric field strength and with concentrations of the particles. The effect of high temperature on ER activity of purrfice/silicone oil systems was also investigated.     

壳聚糖电流变体的导电特性

电流变体是由高介电颗粒分散在低介电油相中组成的悬浮液,在电场作用下,其表观粘度急剧增大甚至发生固化,这种转变过程速度快（达毫秒级）而且是可逆的［１］．由于这种独特的电场响应性,电流变体有广阔的工程应用前景．但电流变体在显示电流变效应的同时也表现出复杂...