Dielectric Behavior of Natural Rubber Composites in Microwave Fields

In this article, we report the preparation of conducting natural rubber (NR) with polyaniline (Pani). NR was made into a conductive material by the compounding of NR with Pani in powder form. NR latex was made into a conductive material by the in situ polymerization of aniline in the presence of NR latex. Different compositions of Pani- NR semi-interpenetrating networks were prepared, and the dielectric properties of all of the samples were determined in microwave frequencies. The cavity perturbation techpique was used for this study. A HP8510 vector network analyzer with a rectangular cavity resonator was used for this study. S bands 2-4 GHz in frequency were used. Thermal studies were also carried out with thermogravimetric analysis and differential scanning calorimetry.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Elastomeric Composites Based on Ethylene-Propylene-Diene Monomer Rubber and Conducting Polymer-Modified Carbon Black

Thermally stable elastomeric composites based on ethylene-propylene-diene monomer (EPDM) and conducting polymer-modified carbon black (CPMCB) additives were produced by casting and crosslinked by compression molding. CPMCB represent a novel thermally stable conductive compound made via ""in situ"" deposition of intrinsically conducting polymers (ICP) such as polyaniline or polypyrrole on carbon black particles. Thermogravimetric analysis showed that the composites are thermally stable with no appreciable degradation at ca. 300 degrees C. Incorporating CPMCB has been found to be advantageous to the processing of composites, as the presence of ICP lead to a better distribution of the filler within the rubber matrix, as confirmed by morphological analysis. These materials have a percolation threshold range of 5-10 phr depending on the formulation and electrical dc conductivity values in the range of 1 x 10(-3) to 1 x 10(-2) S cm(-1) above the percolation threshold. A less pronounced reinforcing effect was observed in composites produced with ICP-modified additives in relation to those produced only with carbon black. The results obtained in this study show the feasibility of this method for producing stable, electrically conducting composites with elastomeric characteristics. POLYM. COMPOS., 30:897-906, 2009. (C) 2008 Society of Plastics Engineers

Structure of polyaniline formed in different inorganic porous materials: A spectroscopic study

In this work, the electronic and structural characterization of polyaniline (PANI) formed in cavities of zeolites Y (ZY) and Mordenite (MOR) and montmorillonite (MMT) clay having Cu(II) as oxidant agent are presented. The formation of PANI and its structure is analyzed by Resonance Raman, UV-Vis-NIR, FT-IR and N K XANES techniques. In all cases the structure of PANT formed is different from the ""free"" polymer. The presence of azo bonds linked to phenazine-like rings are observed only for PANI-MMT composites, independent of the kind of oxidant agent employed in the synthesis. The presence of Cu(II) ions leads to the formation of Phenosafranine-like rings. The presence of these phenazine-like rings in the structure of confined PANT chains can also contribute to the enhancement of the thermal stability observed for all composites. (C) 2008 Elsevier Ltd. All rights reserved.

Charge-transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E(laser) = 1.17 eV suggest that a charge-transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright (C) 2010 John Wiley & Sons, Ltd.

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

Influence of Reaction Conditions on Synthesis of PAni/MnO(2) Composites

An investigation of the parameters as aniline: MnO(2) and temperature on synthesis of polyaniline/MnO(2) composites was performed. The composites were chemically prepared in H(2)SO(4) media using different aniline: MnO(2) ratios at 0 degrees C. After the ratio optimization, the syntheses were performed at 20 degrees C. The polyaniline/MnO(2) composites were characterized by scanning electron microscopy (SEM), ultraviolet-visible, near infrared and infrared spectroscopic techniques. Composites obtained with a uniform, homogeneous and thicker coating of polyaniline films under oxide was considered as the best condition for synthesis.

Photopyroelectric spectroscopy of polyaniline films

Photopyroelectric spectroscopy (PPES), in the 400 < lambda < 900 nm wavelength range, was used to study thermal properties of differently doped polyaniline (PAN) films. The photopyroelectric intensity signal V-n(lambda) and its phase F-n(lambda) were independently measured, as well as the intensity V-n(f) and the phase F-n(f) (f being the chopping frequency) for a given A of the saturation part of the PPES spectrum. Equations of both the intensity and the phase of the PPES signal, taking into account the thermal and the optical characteristics of the PAN films and the pyroelectric detector, were used to fit the experimental results. From the fittings we obtained, with great accuracy, the values of thermal conductivity k and thermal diffusivity coefficient a of PAN films of different doping degrees. It was observed that, in contrast with the strong doping-dependence of the electrical conductivity, the thermal parameters of PAN films remained practically unchanged under doping. This apparent discrepancy is explained by the granular metal model of doped PAN. (C) 2000 John Wiley & Sons, Inc.

Thermo-analyses of polyaniline and its derivatives

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structure and properties of conducting bacterial cellulose-polyaniline nanocomposites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comparison between different conditions of the chemical polymerization of polyaniline on top of PET films

Composites produced during the in situ chemical polymerization of aniline on top of a poly(ethylene terephthalate) (PET) film, in different conditions, were studied by open-circuit potential (Voc), ultraviolet-visible, and infrared spectroscopy, electrical conductivity measurements, scanning electron microscopy, and atomic force microscopy. The polymerization monitoring by Voc showed a maximum associated with the intermediate pernigraniline oxidation state and a final formation of polyaniline (PANI) in the doped emeraldine salt (ES) form. Furthermore, high electrical conductivity values were obtained for the PANI-ES coating prepared under selected conditions. A globular formation was observed for the doped PANI-ES coating with globules of sizes of the same order and same shape of the PET, demonstrating the influence of the substrate on the coating morphology.

Conductive nanocomposites based on cellulose nanofibrils coated with polyaniline-DBSA via in situ polymerization

Cellulose nanofibrils (CNF) were extracted by acid hydrolysis from cotton microfibrils and nanocomposites with polyaniline doped with dodecyl benzenesulphonic acid (PANI-DBSA) were obtained by in situ polymerization of aniline onto CNF. The ratios between DBSA to aniline and aniline to oxidant were varied in situ and the nanocomposites characterized by four probe DC electrical conductivity, ultraviolet-visible-near infrared (UV-Vis - NIR) and Fourier-transform infrared (FTIR) spectroscopies and X-ray diffraction (XRD). FTIR and UV-Vis/NIR characterization confirmed the polymerization of PANI onto CNF surfaces. Electrical conductivity of about 10 -1 S/cm was achieved for the composites; conductivity was mostly independent of DBSA/aniline (between 2 and 4) and aniline/oxidant (between 1 and 5) molar ratios. X-ray patterns of the samples showed crystalline peaks characteristic of cellulose I for CNF samples, and a mixture of both characteristic peaks of PANI and CNF for the nanocomposites. Field emission scanning electron microscopy (FESEM) characterization corroborated the abovementioned results showing that PANI coated the surface of the nanofibrils. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparation and characterization of poly(vinyl butyral)-polyaniline-montmorillonite nanocomposites

Poly(vinyl butyral)-polyaniline-sodium montmorillonite nanocomposites were prepared via polymerization of aniline between clay mineral platelets at two different pH levels (2.0 and 5.0), followed by dispersion of the polyaniline-sodium montmorillonite nanocomposite in a poly(vinyl butyral) solution. A comparison was made of the effect of the pH levels and the polyaniline-sodium montmorillonite nanocomposite precursor on the final structures of the poly(vinyl butyral) nanocomposites and their electrical conductivities. X-ray diffraction patterns revealed the formation of nanocomposites at both pH levels. UV-Vis spectra indicated that the polyaniline formed at both pH levels was conductive, with the UV-Vis spectra presenting a band at 420 nm corresponding to the polaronic form and the beginning of a new band at 600 nm indicating the presence of polaronic segments. FTIR spectra revealed the peaks of the groups present in polyaniline and poly(vinyl butyral) nanocomposites. The electrical conductivities of the polyaniline and poly(vinyl butyral) nanocomposites prepared at pH 2.0 were lower than those of the same nanocomposites prepared at pH 5.0, probably due to the lower formation of polyaniline chains in a more acidic dispersion and to the final configuration of polyaniline in the nanocomposites.

Stabilization of polyaniline by the incorporation of magnetite nanoparticles

Nanocomposites obtained from the polymerization of aniline in the presence of nanoparticles of magnetite (Fe3O4) have been investigated in previous studies. However, there is a lack of information available on the redox interaction of the nanoparticle/conductive polymer couple and the stability that such an oxide can give to the organic phase. In this work, Fe3O4 nanoparticles were incorporated into a PANi matrix by the in-situ oxidative polymerization method. A combination of X-ray diffraction, Mossbauer spectroscopy, transmission electronic microscopy, UV-visible spectroscopy as well as the cyclic voltammetric and Raman spectroscopy techniques, was used to understand the redox effect that the partially oxidized nanoparticles produced on the polymer. It was found that magnetite greatly stabilised PANi, mainly by enhancing the Leucoemeraldine/Emeraldine redox couple and also by reducing the bipolaronic state. (C) 2011 Elsevier B.V. All rights reserved.