Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Electrical and structural analysis of conductive polyaniline/polyimide blends

Conducting films of dodecylbenzenesulfonic (DBSA)‐doped polyaniline/polyimide (PANI/PI) blends with various compositions were prepared by solvent casting followed by a thermal imidization process. Electrical and physical properties of the blends were characterized by infrared spectroscopy, an X‐ray diffraction technique, thermal analysis, a UV‐vis spectrophotometer, a dielectrometer, and conductivity measurements. The blends exhibited a relatively low percolation threshold of electrical conductivity at 5 wt % PANI content and showed higher conductivity than that of pure DBSA‐doped PANI when the PANI content exceeded 20 wt %. A lower percolation threshold and a lower compatibility was shown between the two components in the blends than those of PANI–camphorsulfonic acid/polyamic acid (PANI–CSA/PAA). A well‐defined layered structure due to the alignment of the long alkyl chain dopant perpendicular to the PANI main chain was evidenced by WAXD spectra. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2169–2178, 1999     

Electrical properties of polyaniline–polystyrene blends above the percolation threshold

Blends of conductive polymers with classical ones can exhibit good mechanical properties and good electrical conductivity and deserve great attention for application in electronic industrial technology. Conductive polyaniline solutions have been chemically prepared using bis(2-ethyl hexyl)hydrogen phosphate (DiOHP) as the dopant chemical species. The codissolution method leads to conductive polyaniline–polystyrene (PANI–PSt) composites with good mechanical properties. The dependence of electrical conductivity on the volume fraction of PANI in the blend is found to be characteristic of a percolation system. Electrical conductivity and thermoelectric power measurements are interpreted on the basis of hopping mechanisms between polaronic clusters. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1205–1208, 1998     

Preparation of polyaniline and studying its electrical conductivity

Polyaniline was prepared by chemical methods. Its electrical conductivity was measured. The electrical conductivity of polyaniline salt and polyaniline base were compared with composites prepared by the hot press of polyaniline base with KBr, Co(CH₃COO)₂, and picric acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1658–1665, 2000     

Polyaniline/PVAc blends: Variation with time of structure and conductivity of films cast from aqueous dispersions

Recently, a polymerization process of Anilinium‐Dodecyl Benzene Sulfonic Acid (DBSA) complex in an aqueous dispersion was developed in our laboratories. Simple mechanical mixing of the aqueous PANI–DBSA dispersion with a PVAc aqueous latex leads to highly conductive blends at low PANI–DBSA contents. The percolation threshold of the dried films is extremely low (∼0.5 wt %). The combined aqueous PVAc/PANI–DBSA dispersions exhibit a gradually decreasing electrical conductivity accompanied by a gradually increasing viscosity, with the storage time. However, an aged cast film from these blends maintains its electrical conductivity with time. These phenomena are associated with acidic hydrolytic reactions of the ester group, resulting in the formation of vinyl acetate–vinyl alcohol copolymer and evolution of acetic acid, and also the interaction of the DBSA surfactant with the PVAc, causing swelling and disintegration of PVAc particles. A chemical structural model describing these changes with storage time is suggested. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 760–766, 2001     

Effect of thermal aging on electrical conductivity of the 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid‐doped polyaniline fiber

The thermal characteristics of inherently conductive polyaniline (PANi) fiber have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Fibers show five major weight losses at ∼100°C, 165°C, 215°C, 315°C, and 465°C, which are associated with the removal of moisture, residual solvent, decompositions of the sulfonic acid and degradation of PANi fiber, respectively. The 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPSA) that dopes the PANi (in fiber form) performs two‐stage decompositions. The conductivity of the drawn fibers aged at 50°C, 100°C, 150°C, and 190°C under vacuum for various periods of time decreases, particularly at temperatures higher than 100°C. The reduction in conductivity of the fiber aged at temperatures lower than 100°C is mainly due to the evaporation of the residual solvent (15–20% in the as‐spun fiber). Further decrease in conductivity of the fiber aged at temperatures higher than 100°C is caused by the decomposition of the dopant AMPSA. The temperature‐dependent conductivity of the fiber was measured at 15 K (−258.5°C) to 295 K (21.5°C). The conductivity of both aged and un‐aged fibers is all temperature activated, however, the conductivity of the un‐aged fibers is higher than that of the aged fibers. Although a negative temperature coefficient was observed in the temperature range from 240 K (–24.5°C) to 270 K (–3.5°C) for the un‐aged fibers, it was disappeared when the fibers were thermal aged at 100°C for 24 h in vacuum oven. These results indicate that the residual solvent trapped inside the fiber enhanced the electrical conductivity of the fibers and its “metallic” electrical conductivity at temperatures ∼263 K (–10°C). © 2001 John Wiley & Sons, Inc. † J Appl Polym Sci 79: 2503–2508, 2001     

Effect of annealing on electrical conductivity and morphology of polyaniline films

We report structure–property relationships of polyaniline emeraldine base (EB) films that were produced by combining different processing steps in various sequences. The effect of annealing and doping processes on the surface structure of the films was investigated by atomic force microscopy (AFM), and the corresponding changes to the chemical structure of the EB films were monitored by Fourier transform infrared spectroscopy. AFM results indicate that after doping polyaniline (EB) films with HCl, the root mean square (rms) roughness of the surface of EB film increased ～ 46%. When the doped films were annealed at 180°C under a nitrogen atmosphere for 3 h, the rms roughness was essentially unchanged from that of the initial, undoped films. The electrical conductivity of the films also showed a significant dependence on the processing sequence. When the doped polyaniline (EB) films were annealed, no electrical conductivity was observed. When these films were redoped, only ～ 6% of the initial conductivity could be recovered. In another processing sequence in which the polyaniline (EB) films were first annealed and then doped, the electrical conductivity was only ～ 12% relative to the film that was doped immediately after being cast. From this work, a strategy to reduce the surface roughness of films made from electrically conducting polyaniline (EB) is proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3602–3610, 2001     

Electrical conductivity and electromagnetic interference shielding effectiveness of polyaniline–ethylene vinyl acetate composites

Electrical conductivity and electromagnetic interference (EMI) shielding effectiveness at microwave (200–2000 MHz) and X‐band (8–12 GHz) frequency range of polyaniline (PAni) composites were studied. It has been observed that EMI shielding of conductive polyaniline (PAni)–ethylene vinyl acetate composites increases with the increase in the loading levels of the conductive polymer doped with dodecylbenzene sulfonic acid. The result indicates that the composites having higher PAni loading (>23%) can be used for EMI shielding materials and those with lower PAni loading can be used for the dissipation of electrostatic charge. Copyright © 2004 Society of Chemical Industry     

Thermal and electrical conductivity of carbon–filled liquid crystal polymer composites

The thermal and electrical conductivity of resins can be increased by adding conductive carbon fillers. One emerging market for thermally and electrically conductive resins is for bipolar plates for use in fuel cells. In this study, varying amounts of five different types of carbon, one carbon black, two synthetic graphites, one natural flake graphite, and one calcined needle coke, were added to Vectra A950RX Liquid Crystal Polymer. The resulting composites containing only one type of filler were then tested for thermal and electrical conductivity. The objective of this work was to determine which carbon filler produced a composite with the highest thermal and electrical conductivity. The results showed that composites containing Thermocarb TC‐300 synthetic graphite particles had the highest thermal and electrical conductivity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99; 1552–1558, 2006     

A facile method for synthesis of polyaniline nanospheres and effect of doping on their electrical conductivity

The synthesis of polyaniline (PANI) nanospheres by a simple template-free method has been described. The polymerization of aniline in aqueous medium was accomplished using ammonium persulfate without any protonic acid. The UV-vis spectrum of PANI nanospheres displayed the characteristic absorption peak of π-π* transition of the benzenoid ring at 355 nm. The oxidation state of PANI nanospheres was identified with FT-IR spectroscopy by comparing the two bands at 1582 (ring stretching in quinoid unit) and 1498 cm(-1) (ring stretching in bezenoid unit). The X-ray diffraction patterns demonstrated the low crystalline nature of PANI nanospheres. The morphology of PANI nanospheres was spherical and the mean diameter of nanospheres was found in the range of 3-12 nm. The thermal behavior of PANI nanospheres was studied by thermogravimetric analysis. The effect of doping of HCl and H(2)SO(4) on PANI nanospheres was studied by measuring the current as a function of time of exposure. The high electrical conductivity of 6×10(-2) S cm(-1) was obtained for PANI nanospheres at their optimum doping state by 100 ppm HCl.     

Synthesis,characterization, and electrical conductivity of polyaniline derivatives: Study with the metal ions Cu(II), Ni(II), and Co(II)

Poly(2-aminophenol), poly(3-aminophenol), poly(2-aminobenzyl alcohol), and poly(3-aminobenzyl alcohol) were synthesized by using ammonium persulphate as oxidizing reagent in HCl and HCl/CH₃CN mediums in the presence and absence of Cu(II), Ni(II), and Co(II) ions. The polymers were characterized by Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy, thermal analysis, and electrical conductivity measurements. The substituent in 2- and 3-positions decreases the yield regarding aniline. Poly(2-,3-aminobenzyl alcohol) are obtained in an intermediate redox state and polymerized as aniline. On the contrary, poly(aminophenols) are obtained as overoxidated structures. The presence of metal ion produces an important increase of the polymerization yield. The metal cations would act as oxidizing agents. The incorporation of these metal ions depends on the reaction medium. The metal ion increases the thermal stability. Poly(2-aminobenzyl alcohol)-copper ions also increases the electrical conductivity. The electrical conductivity is higher by acid doping than by the incorporation of metal ions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 330–337, 2001     

New in situ Blends of Polyaniline and Cardanol Bio‐Resins

Cardanol, a well known natural resource, was used to produce a polymer resin in the presence of formaldehyde, catalyzed by H₂SO₄. Before reticulation, PAni · H₂SO₄ was blended with the resin. The blended material was cast into poly(propylene) cups and kept inside a desiccator under vacuum until complete water evaporation. The final in situ polymer blend was solid and could not be dissolved in ordinary solvents, indicating that a reticulated material had been obtained. Samples prepared similarly were then characterized, showing that the produced blends can be used as pressure sensing materials.

     

Electrically conducting polyaniline–poly(acrylic acid) blends

We report an electrically conducting polyaniline–poly(acrylic acid) blend coatings prepared by mixing the emeraldine base (EB) form of polyaniline (PANI) and poly(acrylic acid) (PAA) aqueous solution. The samples show a moderate electrical conductivity σ. If they are immersed in an HCl aqueous solution, the conductivity of the samples is increased by two or three orders of magnitude and their thermal stability is also improved. Optical transmittance spectra show a complete protonation of PANI–PAA blends after immersion in HCl aqueous solution. Fourier transform infrared spectroscopy studies indicate that the better thermal stability of σ could come from the more stable protonated imine nitrogen ions. A low percolation threshold phenomenon is observed in PANI–PAA blends, from a strong interaction between the carboxylic acid groups of PAA and the nitrogen atoms of PANI. © 1998 SCI.     

Polyaniline/zeolite LTA composites and electrical conductivity response towards CO

Electrical conductivity response of polyaniline/zeolite composites towards CO is investigated in terms of dopant type, dopant concentration, zeolite LTA content and zeolite pore size. Both MA and HCl doped polyanilines respond with comparable magnitudes towards CO; the latter responses are slightly smaller for the same doping level. Addition of zeolite 4A reduces the electrical conductivity response but improves the sensitivity towards CO with increasing zeolite concentration up to 40% w/w. This concentration is evidently below the percolation threshold value, which is estimated to be above 50% w/w. Composite with zeolite 3A has a comparable sensitivity value relative to that of pure polyaniline. Composites of 4A and 5A have greater sensitivity values over that of the pure polyaniline at the CO concentration range between 16 and 1000 ppm. Zeolite 5A is the most effective mesoporous material in promoting interaction between CO and polyaniline because of its largest pore size of 5 Å, relative to the zeolite 3A and 4A which have the pore sizes of 4 and 3 Å, respectively.     

Surfactant‐assisted processing of polyimide/multiwall carbon nanotube nanocomposites for microelectronics applications

The dispersion and stability of carbon nanotubes (CNTs) inside a polymer matrix, especially with a high CNT content, are still big challenges. Moreover, the interaction between CNTs and the polymer matrix should be strong enough to improve the mechanical properties. The efficient dispersion of CNTs is essential for the formation of a uniform distribution of a CNT network in a polymer composite. Polyimide/multiwall CNT nanocomposites were synthesized by in situ polymerization with the aid of a surfactant. A Fourier transform infrared spectroscopy study proved that the surfactant did not hamper the polymerization of the polyimide. The microstructure, storage modulus and electrical conductivity of the nanocomposites were improved using a particular amount of the surfactant. Environmental stability test results showed that the polyimide with 1 wt% of CNTs produced with the aid of the surfactant possessed excellent reliability in high‐temperature and high‐humidity environments. Surfactants were successfully used to obtain fine‐structure polyimide/CNT nanocomposites by in situ polymerization. The enhancement of the mechanical properties was attributed to the incorporation of the surfactant. A percolation of electrical conductivity could be achieved with 1 wt% of CNTs. Copyright © 2010 Society of Chemical Industry     

Synthesis, proton conductivity and methanol permeability of a novel sulfonated polyimide from 3-(2′,4′-diaminophenoxy)propane sulfonic acid

A novel sulfonated diamine monomer, 3-(2′,4′-diaminophenoxy)propane sulfonic acid (DAPPS), was successfully synthesized and the sulfonated polyimide (SPI) was prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and DAPPS. The resulting SPI, NTDA-DAPPS, was soluble in common organic solvents. The SPI membrane displayed proton conductivity σ values of 0.12-0.35 S/cm at temperatures ranging from 35 to 90 °C in liquid water, which were similar to or higher than those of Nafion 117 and sulfonated hydrocarbon polymers. The σ of the SPI membrane decreased significantly with decreasing relative humidity (RH) and became much lower than that of Nafion 117 at 30% RH. The SPI membrane displayed good water stability at 80 °C and was thermally stable up to 240 °C. It showed reasonable mechanical strength of a modulus of 1.3 GPa at 90 °C and 90% RH. Its methanol permeability P_M was 0.57×10⁻⁶ cm²/s at 30 °C and 8.6 wt% methanol in feed, which was a fourth of that of Nafion 117. As a result, its ratio of σ/P_M was 21×10⁴ S cm⁻³ s, which was about 4 times larger than that of Nafion 117, suggesting potential application of the SPI membrane for direct methanol fuel cell.     

Synthesis of nano‐sized ZnO and polyaniline‐zinc oxide composite: Characterization,stability in terms of DC electrical conductivity retention and application in ammonia vapor detection

Nano‐sized particles of Zinc oxide (ZnO) were synthesized using a new chemical rout. The chemical oxidative polymerization of aniline in the presence of nano ZnO was employed to synthesize a polyaniline‐zinc oxide (PANI‐ZnO) nanocomposite. The material was characterized by using transmission electron microscopy, XRD, scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), and Thermogravimetric analysis (TGA). The conductivity measurements showed the resulting composites possessed higher conductivity as compared to pure polyaniline (PANI). The nanocomposite exhibited fairly sensitive towards solution of aqueous ammonia (NH₃), when it was exposed to various concentrations of NH₃ in an ambient room temperature. The results show that the sensor has good sensitivity and good repeatability upon repeated exposure to NH₃. PANI‐ZnO nanocomposite was also used to study electrical conductivity under isothermal conditions in the temperature range 50–130°C. The composite was found stable under ambient conditions below 90°C in terms of DC electrical conductivity retention. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Increased electrical conductivity and the mechanism of samarium‐doped ceria/Al2O3 nanocomposite electrolyte

To further enhance the electrical conductivity of doped ceria, the samarium‐doped ceria (SDC)/Al₂O₃ nanocomposites were prepared through sintering the coprecipitated powders in 1100°C‐1300°C. The grain sizes of all composites are less than 100 nm and decrease with alumina addition. Besides the main phases of SDC and Al₂O₃, the SmAlO₃ can precipitate in the composites if sintered at higher temperatures or for longer dwell time. The deviations of SDC diffraction peak positions demonstrate the solid solution of alumina into SDC lattice. The total electrical conductivities of the composites increase with alumina content until 30% alumina is added. The SDC/30%Al₂O₃ presents the higher total conductivity than the pure SDC by about five times. Specifically, the grain interior conductivity generally decreases with the alumina addition while the grain‐boundary conductivity increases with that. The introduction of the conductive SDC/Al₂O₃ interface can contribute to the rise of total conductivity, yet the excessive alumina addition also blocks the oxygen ion conduction. The SmAlO₃ precipitation is detrimental to the ion conduction for it consumes part of alumina and leads to the decrement in Sm concentration of SDC grain. Appropriate alumina addition not only enhances the conductivity of SDC but also lowers the material cost.     

The CO–H2 and CO–H2O reactions over TiO2 nanotubes filled with Pt metal nanoparticles

We have investigated the catalytic behavior of Pt encapsulated TiO₂ nanotubes for the water gas shift reaction as well as the hydrogenation of CO. Pt–TiO₂ nanotube catalysts were prepared by employing fine fiber shaped crystals of [Pt(NH₃)₄](HCO₃)₂ complex as a structure determining template material. The turnover frequencies (TOF) of these nanotube catalysts were more than one order of magnitude larger than conventional impregnation Pt/TiO₂ catalysts, and the selectivity for methanol in CO–H₂ reaction was extraordinary high compared to the impregnation catalysts. The XPS and XRD analyses of the nanotubes revealed characteristic electronic state of reduced TiO₂ (Ti³⁺ in rutile structure) with zerovalent Pt even after the calcination at 773 K. In WGS reaction, electron rich Ti³⁺ on the nanotube wall may play an important role to activate water molecules for the oxidation of CO. In CO–H₂ reaction, similar promotion effect of Ti³⁺ species may be operating for selective methanol formation by supplying active OH(a).     

Thermal behavior of polyaniline films and polyaniline–polystyrene blends

In this article, a study of the thermal behavior of polyaniline films and polyaniline–polystyrene blends is presented. Transport measurements (electrical conductivity and thermoelectric power) at high temperature and thermogravimetric analysis show that an irreversible degradation is observed near 450 K for films doped with DiOHP and near 500 K for films doped with CSA. In both cases, the thermoelectric power is the most sensitive parameter to electrical degradation during the heating of conducting films. Electrical conductivity measurements during heating–cooling cycles show a diminution of the room temperature conductivity after evaporation of the solvent (water, m‐cresol). A model of cluster with a variable diameter allows interpreting this phenomenon by assuming the existence of a sensitive frontier to the solvent at the periphery of conducting clusters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1848–1855, 2002; DOI 10.1002/app.10468