New Approach to Enhance the Yield Stress of Electro‐Rheological Fluids by Polyaniline‐Coated Layered Silicate Nanocomposites

We synthesized new polyaniline (PANI)/organoclay (aminosilane surface‐treated) nanocomposite particles and prepared electro‐rheological (ER) fluids by dispersing the particles in silicone oil. A distinct enhancement in yield stress was observed due to the presence of PANI‐coated clay particles. The effects of delaminated clay on the ER yield stress were investigated and compared with other ER fluid systems, which use PANI particles only or a simply intercalated PANI/clay nanocomposite.     

Electrorheological suspensions of laponite in oil: rheometry studies

We have studied the effect of an external direct current (DC) electric field ( approximately 1 kV/mm) on the rheological properties of colloidal suspensions consisting of aggregates of laponite particles in a silicone oil. Microscopy observations show that, under application of an electric field greater than a triggering electric field Ec approximately 0.6 kV/mm, laponite aggregates assemble into chain- and/or columnlike structures in the oil. Without an applied electric field, the steady-state shear behavior of such suspensions is Newtonian-like. Under application of an electric field larger than Ec, it changes dramatically as a result of the changes in the microstructure: a significant yield stress is measured, and under continuous shear the fluid is shear-thinning. The rheological properties, in particular the dynamic and static shear stress, were studied as a function of particle volume fraction for various strengths (including null) of the applied electric field. The flow curves at constant shear rate can be scaled with respect to both the particle fraction and electric field strength onto a master curve. This scaling is consistent with simple scaling arguments. The shape of the master curve accounts for the system's complexity; it approaches a standard power-law model at high Mason numbers. Both dynamic and static yield stresses are observed to depend on the particle fraction Phi and electric field E as PhibetaEalpha, with alpha approximately 1.85 and beta approximately 1 and 1.70 for the dynamic and static yield stresses, respectively. The yield stress was also determined as the critical stress at which there occurs a bifurcation in the rheological behavior of suspensions that are submitted to a constant shear stress; a scaling law with alpha approximately 1.84 and beta approximately 1.70 was obtained. The effectiveness of the latter technique confirms that such electrorheological (ER) fluids can be studied in the framework of thixotropic fluids. The method is very reproducible; we suggest that it could be used routinely for studying ER fluids. The measured overall yield stress behavior of the suspensions may be explained in terms of standard conduction models for electrorheological systems. Interesting prospects include using such systems for guided self-assembly of clay nanoparticles.     

Electrorheological properties of polyaniline suspensions: field-induced liquid to solid transition and residual gel structure

Polyaniline (PANI) was synthesized via oxidative coupling polymerization in acid conditions and de-doped in solution of ammonia. The electrorheological (ER) properties of the PANI/silicone oil suspensions were investigated in oscillatory shear as functions of electric field strength, particle concentration, and host fluid viscosity. Consistent with literature, the PANI ER fluid exhibits viscoelastic behavior under the applied electric field and the ER response is strongly enhanced with increasing electric field strength and particle concentration. The dynamic moduli, G' and G' increase dramatically, by 5 orders of magnitude, as the electric field strength is increased to 2 kV/mm. A viscoelastic liquid to solid transition occurs at a critical electric field strength, in the range Ec = 50-200 V/mm, whose value depends on particle concentration and host fluid viscosity. The fibrillar structure formed in the presence of the applied field has a static yield strength tau(y), whose value scales with electric field strength as tau(y) approximately E(1.88). When the field is switched off a residual structure remains, whose yield stress increases with the strength of the applied field and particle concentration. When the applied stress exceeds the yield stress of the residual structure, fast, fully reversible switching of the ER response is obtained.     

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.     

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.     

Preparation and electrorheological property of rare earth modified amorphous BaxSr1-xTiO3 gel electrorheological fluid

In this paper, we present a newly developed rare earth modified amorphous barium strontium titanate (Ba(x)Sr(1-x)TiO3) gel/silicone oil electrorheological (ER) fluid. The ER behaviors of suspensions of pure and rare earth modified amorphous Ba(x)Sr(1-x)TiO3 particles in silicone oil have been investigated under a dc electric field. The shear yield stress of the rare earth modified amorphous BaTiO3 gel/silicone oil ER fluid could reach 14.9 kPa at E=3.5 kV/mm while the leaking current density was very low, about 7.64 microA/cm2. The ER fluids with a higher volume fraction had a higher current density and a higher shear yield stress under the same electric field. The ER fluid has a long-term stability against sedimentation. The problem of caking was not serious and the agglomerated particles could be easily broken up by strongly stirring.     

Synthesis,Characterization and Electrorheological Properties of Polyaniline/Titanate Core-Shell Composite

In this study, a facile method was developed for the preparation of a new conducting polymer composite with core-shell structure. The surfaces of layered titanate (K₂Ti₄O₉) particles were first modified with 3-aminopropyltriethoxysilane, and then a polyaniline/titanate (PANI/K₂Ti₄O₉) composite was synthesized via chemical oxidative polymerization. The resulting composites were characterized by SEM, XRD, FTIR and TG measurements. The results indicated that the PANI deposited on the surface of K₂Ti₄O₉ particles resulted in the formation of the composite with a core-shell structure. TG analysis showed that the composite containing 28.7 wt% PANI had better thermal stability than that of pure PANI. Further, the PANI/K₂Ti₄O₉ composite particles were adopted as a dispersed phase in silicone oil for electrorheological (ER) investigation. Suspension of the composite particles exhibited typical ER behavior subjected to an external electric field under steady and dynamic oscillatory shear.     

蒙脱土/二氧化钛复合颗粒电流变液材料的制备及其性能

利用溶胶-凝胶法制备了一种新型的蒙脱土/二氧化钛(MMT/TiO_2)复合电流变 颗粒材料，FT-IR，XRD，SEM分析表明TiO_2以纳米晶的形态包覆于蒙脱土表面。电 流变性能测试表明，MMT/TiO_2复合颗粒的电流变效应比纯蒙脱土电流变液有显著 提高，当颗粒体积分数为25%，直流电场强度为3kV/mm时，TiO_2质量分数为22.7% 的MMT/TiO_2复合颗粒电流变液的静态屈服应力达8.3kPa，此值约为纯蒙脱土电流 变液的4倍。同时发现TiO_2包覆量对电流变效应有重要影响。     

Synthesis and electrorheological characterization of emulsion polymerized SAN‐clay nanocomposite suspensions

Styrene‐acrylonitrile (SAN) copolymer‐clay nanocomposite was synthesized by emulsion polymerization, which is the easiest method of intercalation (e.g., melt or solution intercalation). Existence of the intercalated polymer was verified by Fourier transform‐infrared spectroscopy and X‐ray diffraction (XRD) analysis. From XRD, we confirmed the insertion of styrene‐acrylonitrile copolymer between the interlayers of clay, whose separation consequently becomes larger than that of the polymer‐free clay. Thermogravimetric analysis showed that the thermal stability of the organic polymers was sustained. Using electrorheological (ER) fluids composed of intercalated particles and silicone oil, we observed typical ER behavior, such as higher shear stress in the presence of an electric field and increasing yield stress with particle concentration. We further observed the critical shear rate at which the ER fluids exhibit pseudo‐Newtonian behavior.     

聚N-甲基苯胺/蒙脱土纳米复合材料的合成及其协同电流变效应

用插层聚合法制备了聚N 甲基苯胺 蒙脱土纳米复合材料微粒 ,通过IR、XRD及TEM对其结构进行了表征 .观察发现聚N 甲基苯胺插入蒙脱土层间后 ,蒙脱土片层间距由 0 96nm扩大至 1 34nm .将其分散在甲基硅油中 (2 0wt% )配制成无水电流变液 ,该复合材料表现出显著的协同效应 ,具有较好的电流变行为 .实验表明在电场作用下聚N 甲基苯胺 蒙脱土纳米复合材料的电流变效应比聚苯胺、蒙脱土都有显著提高 ,在 3kV mm(DC ,74 5s- 1 )时 ,剪切强度达 6 0kPa ;同时抗沉降性极好 ,静置 6 0天沉淀率小于 3% .介电性能测试表明聚N 甲基苯胺 蒙脱土纳米颗粒的介电常数和介电损耗较蒙脱土和聚N 甲基苯胺明显提高 ,电导率也达到了最佳范围 .     

Synthesis and characterization of polyaniline/silicon dioxide composites and preparation of conductive films

The focus of this study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop‐by‐drop and spin coating methods. The electrical conductivities of HCl doped PANI film and PANI/SiO₂ composite films were measured according to the standard four‐point‐probe technique. The composite films exhibited an increase in electrical conductivity over neat PANI. PANI and PANI/SiO₂ composites were also investigated by spectroscopic methods including UV‐Vis, FT‐IR, and Photoluminescence. UV‐Vis and FT‐IR studies showed that SiO₂ particles affect the quinoid units along the polymer backbone and indicate strong interactions between the SiO₂ particles and the quinoidal sites of PANI (doping effect). The photoluminescence properties of PANI and PANI/SiO₂ composites were studied and the PANI/SiO₂ composites showed increased intensity as compared to neat PANI. The increase of conductivity of PANI/SiO₂ composite may be partially due to the doping or impurity effect of SiO₂ where the silicon dioxides compete with chloride ions. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well dispersed and isolated in composite films. Copyright © 2009 John Wiley & Sons, Ltd.     

Study on solvent permeation resistance properties of nylon6/clay nanocomposite

Nylon6/clay nanocomposite is prepared by mixing organized montmorillonite with nylon6 in HAAKE mixer. Solvent permeation resistance of the nanocomposite is measured to estimate the resistance to solvent permeation. The nanocomposite shows resistance to solvent permeation superior to that of pure nylon6. In addition, the clay content was found to significantly influence the solvent permeation resistance of nylon6, and the maximum improvement in barrier properties of nylon6/clay composite was found as the clay content reached an “optimum” value. By using proper composites and processing conditions, the permeation rate of toluene and ethanol in nylon6/clay nanocomposite is about 3 and 4 times slower than that in pure nylon6 at 50 °C. Our investigation indicated that the crystalline property of nylon6 has a strong impact on the sorption and diffusion of small molecules in the polymer. The improvement in solvent barrier properties of nylon6/clay nanocomposite is attributable to incorporation of an impermeable phase such as the layered silicate, improvement in crystallinity and decrease of crystalline dimension, which are evidenced by XRD, AFM, DSC and polarized optical microscopy (POM) studies.     

Studies on the conducting nanocomposite prepared by in situ polymerization of aniline monomers in a neat (aqueous) synthetic mica clay

The in situ polymerization of the anilinium‐intercalated synthetic mica clay can easily result in an intercalated polyaniline (PANI)/clay nanocomposite. The FT‐IR spectra demonstrated a significant shift for ν_{(C? N)} at 1292 cm^?1 of the templated polymerized and intercalated PANI molecules. A red shift of λ_max for PANI was found from UV–vis spectra. The intercalated PANI also expanded the clay basal spacing seen from WAXD patterns. The degradation rate and temperature of the nanocomposites were found to alleviate and increase compared to neat PANI, respectively. The microscopic examinations including TEM, SEM, and AFM pictures of the nanocomposite demonstrated an entirely different and more compatible morphology. Conductivity of nanocomposite gradually increased with PANI and apparent increase was found when intercalated PANI content reached 40.6 wt %, the possible percolation threshold. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1800–1809, 2008     

Electrorheological characteristics of polyaniline/titanate composite nanotube suspensions

In this paper, one-dimensional polyaniline/titanate (PANI/TN) composite nanotubes were synthesized by in situ chemical oxidative polymerization directed by block copolymer. These novel nanocomposite particles were used as a dispersed phase in electrorheological (ER) fluids, and the ER properties were investigated under both steady and dynamic shear. It was found that the ER activity of PANI/TN fluids varied with the ratio of aniline to titanate, and the PANI/TN suspensions showed a higher ER effect than that made by sphere-like PANI/TiO₂ nanoparticles. These observations were well interpreted by their dielectric spectra analysis; a larger dielectric loss enhancement and a faster rate of interfacial polarization were responsible for a higher ER activity of nanotubular PANI/TN-based fluids.     

Polyaniline-coated coconut fibers: Structure,properties and their use as conductive additives in matrix of polyurethane derived from castor oil

Electrically conducting fibers based on coconut fibers (CF) and polyaniline (PANI) were prepared through in situ oxidative polymerization of aniline (ANI) in the presence of CF using iron (III) chloride hexahydrate (FeCl_3.6H₂O) or ammonium persulfate (APS) as an oxidant. The PANI-coated coconut fibers (CF-PANI) displayed various morphologies, electrical conductivities and percentages of PANI on the CF surface. For both systems, a PANI conductive layer was present on the CF surface, which was responsible for an electrical conductivity of around 1.5 × 10⁻¹ and 1.9 × 10⁻² S cm⁻¹ for composites prepared with FeCl₃.6H₂O and APS, respectively; values that are similar to that of pure PANI. In order to modify the structure and properties of polyurethane derived from castor oil (PU) both CF-PANI and pure PANI were used as conductive additives. The PU/CF-PANI composites exhibited higher electrical conductivity than pure PU and PU/PANI blends. Additionally, the PU/CF-PANI composites showed a variation in electrical resistivity according to the compressive stress applied, indicating that these materials could be applied for pressure-sensitive applications.     

Synthesis and electrorheological characteristics of sea urchin-like TiO<Subscript>2</Subscript> hollow spheres

TiO₂ hollow microspheres with sea urchin-like hierarchical architectures were synthesized by a simple hydrothermal method. The as-synthesized hollow microspheres with hierarchical architectures consisting of many rhombic building units exhibit high specific surface area. Electrorheological (ER) properties of hierarchical hollow TiO₂-based suspension were investigated under steady and oscillatory shear. The hollow TiO₂-based suspensions show much higher yield stress and elasticity than pure TiO₂ suspension at the same electric field strength. This phenomenon was elucidated well in view of their dielectric spectra analysis. The sea urchin-like architectures result in stronger interfacial polarization of hollow TiO₂ suspension upon an electric field, showing higher ER activity. Also, hollow interiors of TiO₂ particles increase the long-term stability of suspensions and further merit the ER effect.     

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.     

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.     

Electrically developed morphology of carbon nanoparticles in suspensions monitored by in situ optical observations under sinusoidal electric field

In situ optical observations were performed for suspensions composed of carbon nanoparticles under the sinusoidal electric field with an amplitude around 20 kV/mm (volt per micrometer) and various frequencies. For extremely diluted suspensions of mixed fullerenes or multiwalled carbon nanotubes (MWNTs) in a silicone oil, the dark-field optical microscopy was effective for the in situ observation of the particle behavior under the electric field. The nanoparticles in a fullerene suspension under the sinusoidal electric field with a frequency of 100 Hz (in short, 100 Hz electric field) were aggregated to form a rigid spherical microstructure around the halfway between the electrodes. On the other hand, the nanoparticles in an MWNT suspension under 100 Hz electric field were also aggregated but aligned to form a chain-like microstructure which spans the electrodes. Both of the aggregated particles were stable even after the removal of the electric field, and they were redispersed by application of 10 Hz electric field.     

The Electrochemical Properties of Nanocomposite Films Obtained by Chemical In Situ Polymerization of Aniline and Carbon Nanostructures

Interactions between the π bonds in the aromatic rings of polyaniline (PANI) with carbon nanostructures (CNs) facilitate charge transfer between the two components. Different types of phenyleneamine‐terminated CNs, including carbon nano‐onions (CNOs) and single‐walled and multi‐walled carbon nanotubes (SWNTs and MWNTs, respectively), were prepared as templates, and the CN/PANI nanocomposites were easily prepared with uniform core–shell structures. By varying the ratio of the aniline monomers relative to the CNs in the in situ chemical polymerization process, the thickness of the PANI layers was effectively controlled. The morphological and electrical properties of the nanocomposite were determined and compared. The thickness and structure of the PANI films on the CNs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and infrared spectroscopy. TEM and SEM revealed that the composite films consisted of nanoporous networks of CNs coated with polymeric aniline. The electrochemical properties of the composites were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. These studies showed that the CN/PANI composite films had lower resistance than pure polymeric films of PANI, and the presence of CNs much improved the mechanical stability. The specific electrochemical capacitance of the CNO/PANI composite films was significantly larger than for pure PANI.