Spectral and electrochemical studies on blends of polyaniline and cellulose esters

Blends of chemically prepared polyaniline emeraldine base (PANi) with cellulose esters were studied as films by UV–visible spectroscopy and cyclic voltammetry. The cellulose esters used were acetate, propionate, acetate butyrate, and acetate hydrogen phthalate. Films were prepared by casting from N‐methylpyrrolidone or formic acid, and the effect of doping by acids on their spectral and electrochemical properties was studied. Similar behavior was observed with the acetate, propionate, or acetate butyrate, with spectral changes on adding acid due to protonation of the PANi. In agreement with previous studies, kinetic measurements on PANi in a cellulose acetate matrix shows a relatively slow spectral change on protonation. In contrast, with cellulose acetate hydrogen phthalate (CAHP), no changes were observed on adding acid, and it is suggested that the hydrogen phthalate group acts as proton donor. This was mirrored by the cyclic voltammetry behavior in hydrochloric acid solution. Electrochemical studies on films of PANi/CAHP blends in different relative proportions in sulfuric acid solution show a marked dependence on the solvent used for casting, with higher currents and better electrical conductivity being observed in films prepared from N‐methylpyrrolidone. This is shown to be due to the presence of PANi particles in the films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2182–2188, 2002     

Electrochemical polymerization of toluene in the mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid

Poly(methylphenylene) (PMeP) films were prepared by direct oxidation of toluene in the mixed electrolytes of boron trifluoride diethyl etherate (BFEE) and trifluoroacetic acid (TFA). The oxidation potential of toluene in pure BFEE was measured to be 1.52 V versus saturated calomel electrode (SCE). This value was much lower than that determined in a neutral medium such as acetonitrile (2.13 V versus SCE). The introduction of TFA into BFEE decreased the oxidation potential of toluene and also improved the properties of as‐formed polymer films. Infrared and Raman spectra confirmed the formation of PMeP films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 189–195, 2004     

On nonaqueous electrochemical behavior of titanium and Ti compounds

In this study, we examined the electrochemical behavior of titanium and Ti⁴⁺ compounds in THF solutions. Tetra butyl ammonium chloride (TBACl) was used as supporting electrolyte in order to increase the ionic conductivity of the solutions. Electrodeposition of pure titanium could not be obtained. A variety of analytical techniques have been used in conjunction with electrochemical methods in order to analyze the reduction process of Ti⁴⁺. These included Raman and UV-vis spectroscopy, ICP and CHNS elemental analyses. Ti⁴⁺ is being reduced to Ti³⁺ in TiCl₄/THF/TBACl solutions.In addition we show that metallic titanium can be electrochemically dissolved from an organo-metallic electrolyte solution comprising EtAlCl₂ and LiCl in THF. The product is Ti⁴⁺. While LiCl is insoluble in THF it reacts with EtAlCl₂ to form ionic species. Hence, these solutions possessed reasonable ionic conductivity.We could not obtain electroactive Ti⁴⁺ with TiBr₄ or TiI₄ as starting materials, in similar solutions.     

Electrical and optical properties of polyaniline with a weblike morphology

We report on the preparation method of nanostructured polyaniline (PANI) via the oxidation polymerization of aniline hydrochloride in the presence of an anionic surfactant. Two solvents with different polarities were used for the synthesis of PANI. The polymers were characterized with ultraviolet–visible, infrared, Raman, and X‐ray photoelectron spectroscopy. The chemical structure derived from the optical characterization techniques and the electrical properties for the two polymers were almost identical. Transmission electron and scanning electron microscopy images revealed the morphological disparity between the PANIs synthesized under different solvent conditions: a microweb of nanofibers versus microtubes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multiwalled carbon nanotubes/polypyrrole/graphene/nonwoven fabric composites used as electrodes of electrochemical capacitor

The reduced graphene oxide/nonwoven fabric (rGO/NWF) composites have been fabricated through heating the NWF coated with the mixture of GO and HONH₂·HCl at 130°C, during which the GO is chemically reduced to rGO. Then the composites of polypyrrole (PPy)/rGO/NWF have been prepared through chemically polymerizing pyrrole vapor by using the FeCl₃·6H₂O adsorbed on rGO/NWF substrate as oxidant. Finally, multiwalled carbon nanotubes (MWCNTs) are used as conductive enhancer to modify PPy/rGO/NWF through dip‐dry process to obtain MWCNTs/PPy/rGO/NWF. The prepared composites have been characterized and their capacitive properties have been evaluated in 1.0M KCl electrolyte by using two‐electrode symmetric capacitor test. The results reveal that MWCNTs/PPy/rGO/NWF possesses a maximum specific capacitance (C_sc) of about 319 F g^?1 while PPy/rGO/NWF has a C_sc of about 277.8 F g^?1 at the scan rate of 1 mV s^?1 and that optimum MWCNTs/PPy/rGO/NWF retains 94.5% of initial C_sc after 1000 cycles at scan rate of 80 mV s^?1 which is higher than PPy/rGO/NWF (83.4%). Further analysis reveals that the addition of MWCNTs can increase the charger accumulation at the outer and inner of the composites, which is favorable to improve the stability and the rapid charge‐discharge capacity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41023.     

Spectroelectrochemical investigations of aniline–thiophene copolymers in acetonitrile

The copolymerization of aniline and thiophene with varying concentration ratios was studied in acetonitrile/tetrabutylammonium tetrafloroborate. In situ UV‐vis and in situ surface resonance Raman spectroscopic studies revealed that polythiophene and polyaniline units of different lengths enter into the electropolymerization products. The copolymers deposited were either polyaniline‐based or polythiophene‐based polymeric structures depending on the initial concentration of the monomers used. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3417–3423, 2003     

In situ electrochemical synthesis of a poly(o‐anisidine) counter electrode for a dye‐sensitized solar cell

Poly(o‐anisidine) (POA) counter electrodes (CEs) were fabricated by potentiodynamic deposition and incorporated into platinum (Pt)‐free dye‐sensitized solar cells (DSSCs). A different sweep number had great impact on the morphology and electrocatalytic activity of the POA films. The POA film fabricated by 25 sweep cycles was observed to have a highly porous morphology, and this resulted in a lower charge‐transfer resistance of 57 cm² in comparison with the Pt CE. The DSSC assembled with the POA CE showed a higher photovoltaic conversion efficiency of 1.67% compared to 1.2% for the DSSC with the Pt CE under full sunlight illumination. Therefore, the high active surface area of the 25‐sweep‐segmented POA film could be considered a promising alternative CE for use in DSSCs because of its high electrocatalytic performance and electrochemical stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42041.     

Poly(ester)s and poly(amide)s with fluorene and diphenyl-silane units in the main chain: Effects of iodine doping on the structure and electrical conductivity

Intramolecular charge transfer interaction between the electron donor and electro acceptor units within the polymeric structure and its optoelectronic properties were studied. The monomer, 9H-fluorene-2,7-dicarboxylic acid, was prepared from 9H-fluorene-2,7-dicarbonitrile using CuCN/N,N-dimethylformamide followed by the decomposition of the complex with FeCl₃x6H₂O in HCl and KOH/H₂O. The formation of two new classes of polymers was reported at different reaction times. The poly(ester) (PEF) was synthesized by the reaction of the diacid monomer with bis(4-hydroxiphenyl)diphenylsilane using tosyl chloride/pyridine/dimethylformamide system as condensing agent. Alternatively, the poly(amide) (PAF) was synthesized by the direct polycondensation of the diacid monomer and bis(4-aminophenyl)diphenylsilane in N-methyl-2-pyrrolidine solution containing dissolved calcium chloride. The resulting new polymers were obtained in good yields and were characterized by FTIR, NMR (¹H, ¹³C, and ²⁹Si), ESI, Raman, UV (optical gap) and fluorescence spectroscopy. The thermal properties were characterized by DSC and TGA. The electrical conductivity of the polymers was measured before and after exposure to iodine vapor, utilizing films of different thickness. Ellipsometric studies were used for the determination of the film thickness. Morphological differentiation was carried out by SEM-EDX analysis. Oxidation of the polymer films of low thickness decreased their conductivities, mainly due to the small structural changes. For a polymeric sample with a higher thickness, the doping process slightly increased the conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrodeposition of High-quality Polycarbazole Films in Composite Electrolytes of Boron Trifluoride Diethyl Etherate and Ethyl Ether

High-quality polycarbazole (PCZ) films were synthesized electrochemically by direct oxidation of carbazole in boron trifluoride diethyl etherate (BFEE) containing vol. 20% ethyl ether (EE). The oxidation potential of carbazole in this medium was measured to be only 0.90 V vs. SCE, which was lower than that determined in acetonitrile containing 0.1 mol l⁻¹ Bu₄NBF₄ (1.35 V vs. SCE). PCZ films obtained from this medium showed better electrochemical behavior, better thermal stability with conductivity of 7.5 × 10⁻³ S cm⁻¹ being one order of magnitude higher than those reported previously, indicating that BFEE/EE was a better medium than acetonitrile for the electrosyntheses of PCZ films. As-formed PCZ films can be partly dissolved in acetone, acetonitrile and tetrahydrofuran. Spectral analysis provided evidence for the existence of the conjugated structure of the PCZ chain. Fluorescent spectra indicate that electrosynthesized PCZ is an ideal blue light emitter.     

In situ fluorescence spectroscopic studies of polymerization of anaerobic adhesives

Anaerobic adhesives cured by a redox initiated free radical mechanism contain acrylate monomers, stabilizers, accelerators, a nonreactive fluorophore used as an inspection aid, and various nonreactive ingredients to modify polymer properties and rheology. Fluorescence spectroscopy has shown that collisional quenching of the fluorophore due to an amine cure‐accelerator is reduced by rising viscosity during polymerization, thus resulting in an increase in fluorescence intensity. By monitoring the changes in fluorescence intensity with an in situ fiber‐optic method, room temperature polymerizations have been characterized both in a model formulation containing only reactive ingredients as well as in a real commercial formulation containing many nonreactive ingredients. The results from this fluorescence method on polymerization monitoring show excellent correlation with the FTIR results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Impact damage sensing of multiscale composites through epoxy matrix containing carbon nanotubes

Carbon nanotubes are used to provide increased electrical conductivity for polymer matrix materials, thus offering a method to monitor the structure's health. This work investigates the effect of impact damage on the electrical properties of multiscale composite samples, prepared with woven fiberglass reinforcement and epoxy resin modified with as‐received multi‐walled carbon nanotubes (MWCNTs). Moreover, this study addresses potential bias from manufacturing, and investigates the effectiveness of resistance measurements using two‐ and four‐point probe methods. Transmission electron microscopy and static tensile tests results were used to evaluate, respectively, the dispersion of MWCNTs in the epoxy resin and the influence of the incorporation of these nanoparticles on the static tensile properties of the matrix, and interpret results from the resistance measurements on impacted specimens. In this study, the four‐point probe method is shown to be much more repeatable and reliable than the two‐point probe method. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Raman spectroscopic studies on the structural changes of electrosynthesized polypyrrole films during heating and cooling processes

Polypyrrole films were electrochemically synthesized by direct oxidative polymerization of pyrrole in acetonitrile containing β‐naphthalene sulfonic acid or tetrabutylammonium tetrafluoroborate as an supporting electrolyte. We characterized the as‐grown polypyrrole films by resonance Raman spectroscopy in the temperature region of ?195 to 275°C. During the heating process, the Raman bands related to the oxidized species decreased gradually, due mainly to the affect of oxygen and moisture in the air, and, finally, the neutral polymer chains decomposed into disordered carbons. During the cooling process, polymer chains changed from disordered (coil‐like) to ordered (rodlike) structures and caused the elongation of the conjugated chain length. This results in a red shift of the absorption of the electron spectra of the polymer and the enhancements of the Raman bands related to the oxidized species. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3390–3395, 2003     

In situ determination of aniline polymerization kinetics through near‐infrared spectroscopy

This article describes a method for the determination of kinetic constants in aniline polymerizations performed in the presence of dodecylbenzene sulfonic acid. The procedure was based on the measurement of light absorbances at 668 and 1026 nm. The absorption at 668 nm is related to pernigraniline formation and is ordinarily used for ultraviolet–visible kinetic studies. The absorption at 1026 nm is related to the second overtone of the N? H bonds, which may be used to monitor the aniline consumption along the reaction time. Tzou and Gregory's empirical reaction model was used as a reference for kinetic studies. The best fits were obtained when the kinetic constants were evaluated at 1026 nm because of the lower noise/signal ratio in this spectral region and the smaller sensitivity to the pernigraniline/emeraldine transition during the last stages of the polymerization. The remarkable innovation supplied by this study is the possibility to study aniline polymerizations in situ in realistic reaction conditions, which will allow the use of concentrated monomer solutions, large reaction volumes, efficient cooling conditions, and agitation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In situ synthesis of cabbage like polyaniline@hydroquinone nanocomposites and electrochemical capacitance investigations

A Cabbage like polyaniline@hydroquinone composite microsphere was synthesized using in situ polymerization and the electrochemical performance was investigated. The core template, p‐benzoquinone, is demonstrated working as an oxidizing agent for the in situ polymerization of PANI, and to be reduced to 1, 4‐hydroquinone after reaction. The morphology and microstructure of samples were examined by field emission scanning electron microscopy, transmission electron microscope, X‐ray photoelectron spectrometer, thermo gravimetric, and Fourier transform infrared spectra. The cyclic voltammetry, impedance and galvanostatic charge/discharge analysis demonstrates that PANI contributes electronic conductive channels for hydroquinone, and hydroquinone works as a pseudocapacitance component. The prepared PANI@hydroquinone nanocomposite exhibits brilliant electrochemical properties of a specific capacitance of 126.0 F g^?1 at a scan rate of 5 mV s^?1 and enhanced stability of about 85.1% of initial capacitance retained after 500 cycles scanning at a current density of 1 A g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42290.     

Ex-situ spectroscopic ellipsometry studies of micron thick CVD diamond films

Micron thick diamond films have been studied by spectroscopic ellipsometry (SE). The films were grown, on previously prepared Si(100) substrates, by the plasma enhanced chemical vapor deposition (PECVD) technique. Ex situ SE measurements were carried out on samples grown under different conditions, such as substrate temperature and methane fraction in the gas mixture. An optical model consisting of five layers was constructed in order to explain the SE spectra and to provide the optical and structural parameters of the films. This model was deduced from results of various measurements performed by other characterization techniques (Raman spectroscopy, scanning electron microscopy, atomic force microscopy and positron annihilation spectroscopy) which have revealed the optical and structural parameters of the samples. Its sensitivity to the surface and interface roughness as well as to the absorption of the nondiamond phase of the film is demonstrated. Several values of the percentage of the nondiamond phase can be obtained, with the same fit quality, however, depending on the amorphous carbon reference used in the model. These references were obtained by performing SE measurements on various amorphous carbon films. Finally, our SE analysis has allowed us to monitor the lateral homogeneity of the thickness, surface and interface roughness and nondiamond phase concentration over the diamond film.     

Electrochemical polymerization of phenanthrene in mixed electrolytes of boron trifluoride diethyl etherate and concentrated sulfuric acid

A novel high‐quality polyphenanthrene (PPH) film with electrical conductivity of 10^?1 S cm^?1 was synthesized electrochemically by direct anodic oxidation of phenanthrene in boron trifluoride diethyl etherate containing 10% concentrated sulfuric acid (v/v). The oxidation onset potential of phenanthrene in this medium was measured to be only 0.91 V versus saturated calomel electrode (SCE), which was lower than that determined in acetonitrile + 0.1 mol L^?1 Bu₄NBF₄ (1.56 V versus SCE). As‐formed PPH films from this medium showed good electrochemical behavior and stability. De‐doped PPH films were thoroughly soluble in dimethylsulfoxide or CHCl₃. The structure and morphology of the polymer were investigated using UV‐visible and Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy. FTIR and ¹H NMR spectra showed that the PPH was grown via the coupling of the monomer mainly at the C₄, C₅, C₉ and C₁₀ positions. Fluorescence spectral studies indicated that PPH was a blue‐green light emitter. Copyright © 2007 Society of Chemical Industry     

Investigation of the behavior of hydrogen‐bonded phenolic compounds and their determination by using poly(vinylferrocenium)–polyaniline composite film

The hydrogen bonding between phenolic compounds (phenol (Ph), catechol (Ct), resorcinol (Rs), and hydroquinone (Hq)) is investigated at pH 4. The oxidation behaviors of total phenolic compounds (TotPh) are different from their individual behaviors due to the existence of intermolecular hydrogen‐bonded oligomeric clusters. Theoretical calculations and voltammetric and spectroscopic evidences support the intermolecular hydrogen bonding. The interaction of the phenolic compounds with polyaniline (PANI) and poly(vinylferrocenium) (PVF⁺) films are also investigated electrochemically and spectroscopically. The phenolic molecules are immobilized in both polymers due to the construction of hydrogen bonds by PANI and the complexation with PVF⁺. In addition, Ct and Hq are catalytically oxidized by PANI. Determinations of Ct and TotPh are performed on PVF⁺–PANI composite ‐ coated Pt electrode using amperometric I–t method. Composite coating exhibits significant electrochemical activity toward Ct and TotPh, with high sensitivity and a wide linearity range. The steady‐state currents versus concentration of Ct and TotPh are found to be linear in the range of 1.35 × 10^?3?50.0 mM and 4.10 × 10^?4?560 mM for two linear regions, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43596.     

Humidity sensing and electrical properties of polyaniline/cobalt oxide composites

Polyaniline/cobalt oxide composites were synthesized by an in situ chemical polymerization method with ammonium persulfate as an oxidizing agent. This was a single‐step polymerization process for the direct synthesis of the emeraldine salt phase of the polymer. The polymers were characterized with X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectral analysis. The formation of mixed phases of the polymer together with the conducting emeraldine salt phase was confirmed by spectroscopic techniques. High‐temperature conductivity measurements showed thermally activated behavior. A change in the resistance was observed with respect to the relative humidity when the pellets were exposed to a wide humidity range of 10–95%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 653–658, 2007     

Preparation and enhanced electrochemical properties of Ag/polypyrrole composites electrode materials

Ag/polypyrrole (PPy) composites were synthesized with different dispersants via interface polymerization method. The morphology of the composites was investigated by scanning electron microscopy and transmission electron microscopy, and the results showed that the dispersant had strong effect on the morphology of the obtained composites. The structure of the products was characterized by Fourier transform infrared spectroscopy, and X‐ray diffraction. The specific capacitance and impedence of Ag/PPy composites electrode was evaluated through charge/discharge measurements and electrochemical impedance spectroscopy, respectively. Electrochemical performances indicated that Ag/PPy composite electrode used polyvinyl alcohol as dispersant exhibited the highest specific capacitance of 635.5 F/g at a current density of 2.45 mA/g, which provided potential application as supercapacitor materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013