Synthesis and electrorheology of camphorsulfonic acid doped polyaniline suspensions

 Semiconducting camphorsulfonic acid doped polyaniline (PANI–CSA) particles were synthesized by chemical oxidation polymerization, and their chemical structure and particle size were examined via Fourier transform IR spectroscopy and scanning electron microscopy, respectively. Electrorheological (ER) fluids were prepared by dispersing the PANI–CSA particles in silicone oil, and their steady-shear rheological properties under electric fields were investigated using a rotational rheometer with a high-voltage generator. The PANI–CSA synthesized in this study possesses typical ER behavior:shear stress increases with increasing electric field strengths. Received: 31 August 2000 Accepted: 6 April 2001     

Effect of polymerization temperature on polyaniline based electrorheological suspensions

As one of the intrinsically polarizable materials used in electrorheological (ER) fluid, polyaniline was synthesized by the chemical oxidation of aniline with ammonium peroxysulfate. ER fluids were prepared by dispersing polyaniline particles in silicone oil, and their rheological properties were measured. The effect of the polymerization temperature of polyaniline on its ER characteristics was investigated. ER fluids with polyaniline particles synthesized at −10°C (PA-10) showed the best ER performance (yield stress) compared with those synthesized at higher temperatures. A difference in the flow behavior of the ER fluids was also investigated through the dielectric spectra of ER fluids. Received: 24 March 1988 Accepted: 3 August 1998     

Polyaniline microsphere encapsulated by poly(methyl methacrylate) and investigation of its electrorheological properties

Microspheres consisting of a poly(methyl methacrylate) (PMMA) shell wrapping the conductive polyaniline (PANI) particle as a core were prepared by an in-situ suspension polymerization method and then adopted as an electrorheological (ER) material. The polymerization reaction and encapsulation were confirmed by Fourier transform infrared spectrum analysis. The rod-like PANI particles were synthesized via an emulsion polymerization protocol and observed by transmission electron microscopy. In addition, a spherical shape of encapsulated PANI/PMMA (core/shell) microspheres was observed by scanning electron microscopy. The thermal stability of PANI/PMMA particles was examined by use of thermogravimetric analysis. The PANI/PMMA particle-based suspension in silicone oil exhibited typical ER behavior. The conductivity of PANI/PMMA particles was much lower than that of the rod-like PANI.     

Synthesis and electrorheological response of nano-sized laponite stabilized poly(methyl methacrylate) spheres

Poly(methyl methacrylate) (PMMA) nanospheres were fabricated via surfactant-free Pickering emulsion polymerization, in which hydrophilic laponite clay was used to stabilize the emulsions of methyl methacrylate dispersed in distilled water. These synthesized PMMA nanoparticles, of which the surface is compactly wrapped by laponite clay, are observed, as confirmed by scanning electron microscopy and transmission electron microscope images. Fourier-transform infrared spectra and thermogravimetry analysis confirm the chemical composition, thermal property, and mass percent of the laponite located on the surface of PMMA particles. Finally, laponite-wrapped nano-sized PMMA spheres were adopted as an electrorheological material. By using an optical microscope, the chain-like structure was observed when an external electric field was applied. In addition, the ER performance was also examined via a rotational rheometer equipped with a high voltage generator.     

Influence of particle concentration on the electrorheological efficiency of polyaniline suspensions

The dependence of the efficiency of positive electrorheological (ER) phenomenon, expressed as a ratio of the low-shear electroviscosity to the field-off viscosity, on the particle concentration of polyaniline base suspensions in silicone oil has been studied. A simple analysis reveals that the dependence of the efficiency on the volume fraction of suspended particles may have a maximum at which the optimum ER performance of material is expected. Experimental results confirmed this expectation. It is demonstrated that with higher temperature the maximum is shifted to higher particle concentration.     

Electrorheological characteristics of polyaniline and its copolymer suspensions with ionic and nonionic substituents

Electrorheological (ER) characteristics of ER fluids, composed of suspensions of semiconducting polyaniline and two different copolyaniline particles in silicone oil, were determined experimentally. Ionic sodium diphenylamine sulfonate and nonionic o-ethoxyaniline were used to synthesize copolyanilines, i.e. N-substituted copolyaniline and poly(aniline-co-o-ethoxyaniline), respectively. ER fluids composed of these three different polymers were compared with respect to their rheological properties under an applied electric field. It was found that ER fluids containing a copolymer with an ionic group exhibited the highest ER performance among polyaniline and its copolymer systems in a shear-rate region above 1 s⁻¹. Received: 22 February 1999 /Accepted in revised form: 25 August 1999     

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.     

Synthesis and characterization of new azobenzenesulfonic acids doped conducting polyaniline

New azobenzene sulfonic acid dopants were synthesized by diazotized coupling reaction of sulphanilic acid diazonium salt with commercially available raw materials such as phenol, m-cresol and 4-phenylphenol. The structures of the dopants are confirmed by NMR and FT-IR. Polyaniline emeraldine base was doped by these new azobenzenesulfonic acid dopants in two different solvent medium such as methanol and N-methylpyrrolidinone to produce green emeraldine salt. The doping process was confirmed by FT-IR and UV-vis spectroscopy. The effect of composition of dopant on the conductivity of the polyaniline was investigated and the results suggest that the conductivity increases with the increase in the dopant concentration and attained maxima for more than 38% in the feed. The conductivity measurements reveal that all the dopants equally effective in producing in high conductivity in the range of 0.02 S/cm and the conductivity of the doped samples are insignificant to the structural difference in the dopant. WXRD and SEM analysis indicate that the doped samples are highly amorphous and porous in nature. The thermal analysis by TGA indicate that all the doped materials were highly stable up to 300 °C for high temperature applications.     

Electrorheological properties of perchloric acid-doped polythiophene suspensions

Poly(3-thiopheneacetic acid), PTAA, was synthesized via an oxidative polymerization and doped with perchloric acid to control its conductivity. The rheological properties of the HClO₄-doped PTAA/silicone oil suspensions were measured in oscillatory shear to investigate the effects of electric field strength, particle concentration, and particle conductivity on electrorheological (ER) characteristics. The PTAA-based ER fluids exhibit viscoelastic behavior under an applied electric field and the ER response is amplified with increase of electric field strength. The dynamic moduli, G and G, increase dramatically by ten orders of magnitude when the field strength is increased to 2 kV/mm. The suspensions exhibit a transition from fluid-like to solid-like behavior as the field strength increases, and reach a saturated ER response at a field strength of 1 kV/mm. Increase of particle concentration and particle conductivity result in a lower transition field strength. Scaling arguments are presented which successfully superpose the scaled moduli at various electric field strengths onto a single master function of the dimensionless frequency.     

苯胺在十二烷基苯磺酸/水体系中的乳液聚合过程研究

利用光学显微镜和扫描电镜,对以水为介质、十二烷基苯磺酸(DBSA)为乳化剂的苯胺乳液聚合过程进行监测,发现苯胺在水体系中与DBSA反应形成DBSA-苯胺盐的棒状聚集结构,讨论了DBSA、苯胺、氧化剂的配比及浓度对聚合过程中棒状聚集结构的长度和数量及生成聚苯胺的电导率的影响,提出苯胺在DBSA/水体系中的乳液聚合反应是在胶束表面进行的,而棒状聚集结构中的DBSA-苯胺盐单体经水相扩散到乳胶粒子中,形成颗粒状的聚苯胺.     

金属核心/高聚物膜复合悬浮相电流变流体材料

针对电流变流体悬浮相材料的开发与研究,根据介质极化原理,设计开发了金属核心/高聚物膜复合悬浮相电流变流体材料,在乳液聚合与微胶囊包覆技术的基础上,制备出了金属核心/高聚物膜复合颗粒.并对这种金属核心/高聚物膜复合颗粒的电流变流体性能进行了测试与研究.从理论和实验上都说明了金属核心/高聚物膜复合悬浮相材料在改善电流变流体力学性能及稳定性方面具有潜力,是可以进一步提高与改进的电流变流体材料.     

Effects of medium oil on electroresponsive characteristics of chitosan suspensions

Biocompatible chitosan particle suspensions in host oils of corn, soybean, and silicone were prepared and their electrorheological (ER) characteristics were examined under the imposition of electric fields. The effects of the weight concentration of particulate chitosan and the strength of the applied electric field on ER response in the various chitosan particle suspensions were investigated via measurements of rheological properties including flow curve, shear viscosity, and yield stress. The yield stresses of the three different chitosan–oil systems showed different values of slope in the electric field, but all data were found to fit well with our previously proposed universal scaling function.     

Differences in the electrorheological response of a particle suspension under direct current and alternating current electric fields

We have observed an unusual reduction of shear stress with increasing shear rate under direct current electric fields, for an electrorheological fluid composed of sulfonated poly(styrene-co-divinylbenzene) particles dispersed in silicone oil. At all shear rates, the shear stress under the electric field is larger than that in the absence of the field, indicating that there is still some field-induced agglomeration of the particles. In contrast, the behavior under alternating current electric fields is the Bingham-fluid-type response commonly observed with electrorheological fluids. It is suggested that the conventional dipole–dipole interaction approach based on simplified microstructural models would be unable to explain these phenomena. Received: 27 November 2000 Accepted: 22 May 2001     

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.     

Comment on “Preparation and electrorheological properties of triethanolamine-modified TiO2”

Comments on the recent report of electrorheological (ER) properties of an organic modified titanium dioxide with considerably high yield stress are given based on the analysis of its yield stress data as a function of applied electric field strengths. Using our previously reported universal yield stress equation and critical electric field strengths deduced, it is found that we can collapse their data onto a single curve.     

Preparation and characterization of anthracenecarboxylic acid doped polyaniline thin films

Doped polyaniline films were prepared with electrochemistry method. A small conjugated molecule, anthracenecarboxylic acid(2-ACA), was used as the dopant, considering its electrical activeness due to the conjugated π-π* structure. Film morphology of doped and undoped polyaniline samples was investigated. The corresponding changes in optical and electrical properties after ACA doping were discussed. By measuring and calculating their energy level distribution, a promising application of polyaniline thin films as buffer layer in optic-electric devices is expectable.     

Synthesis and characterization of glass-containing superabsorbent polymers

By embedding hollow glass spheres of different sizes and densities into a matrix of crosslinked sodium polyacrylate, superabsorbent polymers were synthesized using a water-in-oil suspension polymerization. These glass-containing superabsorbents were capable of taking up water not only in form of a swollen polyacrylate gel, but also in form of additional free water between the glass spheres and the surrounding polyacrylate matrix. According to swelling measurements the maximum volume swelling degree of the glass-containing superabsorbents is in certain cases nearly double as large as the value of a superabsorbent without embedded glass spheres.     

Synthesis,characterization and properties of polyaniline doped with transition metal substituted silicotungstate

Polyaniline hybrid material doped with transition metal mono-substituted silicotungstate β₂-K₆[SiW₁₁M(H₂O)O₃₉]?·?xH₂O (M?=?Mn²⁺, Co²⁺, Cu²⁺, Fe²⁺) were prepared for the first time. Their scanning electron microscopy (SEM), infrared (IR), UV–Vis, and X-ray diffraction (XRD) patterns confirm the existence of Keggin anions and form the space reticular structure. The material exhibits excellent proton conduction, its proton conductivity is 9?×?10^?2?s?cm^?1 at room temperature (20°C).     

不同磺酸掺杂聚苯胺的制备及在超级电容器中的应用

以MnO₂为氧化剂,采用乳液聚合法,用三种不同的磺酸型表面活性剂制备掺杂聚苯胺(PANI)。通过扫描电子显微镜(SEM)、傅里叶变换红外(FTIR)光谱以及X射线衍射(XRD)等手段对其结构及形貌进行表征;用所得的掺杂聚苯胺制作电极,组装成对称扣式超级电容器,用循环伏安法(CV)、电化学阻抗(EIS)和恒电流充放电技术进行电化学性能研究。结果表明,磺酸表面活性剂的引入有利于PANI纳米纤维的形成和分散,掺杂Nafion的PANI纤维直径在30-40 nm之间,纤维交织成多孔的疏松结构;当放电电流为0.1 A·g^-1时,以PANI-Nafion、PANI-SDS(十二烷基磺酸钠)、PANI-SDBS(十二烷基苯磺酸钠)为电极材料的超级电容器比容量分别为385.3、359.7、401.6 F·g^-1,均高于未掺杂PANI的比容量(235.8 F·g^-1);其中, PANINafion的循环稳定性最好, 1000次循环后其比容量保持率高达70.7%。     

Synthesis and characterization of aniline and aniline-o-sulfonic acid copolymers

The copolymer of aniline (An) and aniline-o-sulfonic acid (AS) is synthesized by chemical oxidation polymerization. The effects of mole ratio of copolymerized monomers on chain structure, thermostability, conductivity, redox properties of copolymer are discussed. It is indicated that if more AS monomers in polymerization system the corresponding structure units will increase, but their relation isn’t linear. When An:AS = 1:1, the ratio of structure unit in copolymer is 9:1, and it is only 1:2 for copolymer with An:AS = 1:6. The measurements of conductivity and redox activity also prove that the properties of An-co-AS(1:1), (1:3), and (1:4) are similar to polyaniline due to more An units than AS. When An:AS is higher than 1:6, it shows out the properties of copolymer is similar to those of poly(aniline-o-sulfonic acid), and their redox route is different. They will transform to follow the route of LH ↔ EH ↔ P. The results of thermo-analysis indicate that the decomposition temperature of AS units is lower than An units because of the electron-withdrawing group substitution. The decomposition temperature of polymer is related to dopant and doping degree. Electron-withdrawing group, -SO₃H, substitution and HCl doping will decrease polymer chain decomposition temperature. The mechanism of copolymerization of An and AS is different from homopolymerization. The monomer with low oxidation potential forms free radical cation firstly, which transfers to monomer with higher oxidation potential and initiates its polymerization.