Conduction mechanism in H‐type polysiloxane‐polypyrrole block copolymers

Conducting polymers of polysiloxane‐polypyrrole were synthesized by electropolymerization of the pyrrole monomer through pyrrole moieties in N‐pyrrole‐terminated polysiloxanes. Sodium paratoluene sulfonate was used as the electrolyte. Scanning electron microscopy (SEM) was used to determine the surface morphology of the films. The room‐temperature conductivity values of the films were found to be in the range of 1.9–4.4 × 10^?4 (Ω cm)^?1, depending on the supporting electrolyte concentration. The temperature dependence of the dc conductivities of the copolymers having different dopant concentrations was investigated within the temperature range of 100–320 K. The evaluated parameters showed that the electrical transport is dominated by variable range hopping. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 52–56, 2002     

Optical and electrical characterization of (PEO+methyl violet) polymer electrolytes

Optical properties and electrical conductivity of polyethylene oxide (PEO) with methyl violet dopant film have studied. The complexation of the methyl violet dopant with PEO was confirmed by X‐ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopic studies. The microstructure morphology have been analyzed by scanning electron microscope (SEM) for pure and dopant films. The UV‐absorption studies were made in the wavelength range 190–1100 nm for pure and doped films. The dc electrical conductivity data was collected using two probe technique in the temperature range 303–333 K. The UV–visible spectra showed the absorption band at 190 nm for pure PEO and doped from 208–224 nm region with different absorption intensities. The absorption edge, direct and indirect band gap were estimated using Mott and Davis Model. The optical activation energy can be determined using the Urbach rule, for pure PEO it was found 2.38 eV and 1.28–4.08 eV for doped films. The absorption band was shifted toward the higher frequency, the direct and indirect band gap decreases with increasing of dopant concentration, corresponds to the allowed inter band transition of electron. The dc electrical conductivity results shows that it increases with increasing dopant weight percentage and temperature which corresponds to the enhancement of charge mobility in these dye doped polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Optical and electrical properties of polyaniline‐cadmium sulfide nanocomposite

Polyaniline‐cadmium sulfide nanocomposite has been synthesized by the chemical oxidative polymerization of aniline with ammonium peroxodisulfate as an initiator in presence of cadmium sulfide nanoparticles. TEM, XRD, FTIR, TGA, UV–vis spectroscopy, and photoluminescence studies were done for the structural, thermal and optical characterization of the samples. The particle size of nanocomposites lies in between 7 and 10 nm. XRD spectrum shows that polyaniline is amorphous, but peaks present in the spectrum of polymer nanocomposites are for cadmium sulfide nanoparticles. TGA result shows that nanocomposite is more thermally stable. The band gap of nanocomposite decreases with increasing content of cadmium sulfide nanoparticles. An enhancement in photoluminescence has been observed in the nanocomposite than that in pure polyaniline. The dc and ac electronic transport property of polyaniline cadmium sulfide composites has been investigated within a temperature range 77 ≤ T ≤ 300 K and in the frequency range 20 Hz–1 MHz. The dc conductivity follows variable range hopping (VRH) model. The ac conductivity follows a power law whereas the temperature dependence of frequency exponent s can be explained by correlated barrier hopping (CBH) model. The dielectric behavior of the samples has been explained in terms of the grain and grain boundary resistance and capacitance. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Polymerization of polyaniline under various concentrations of ammonium peroxydisulfate and hydrochloric acid by ultrasonic irradiation

Effects of various molar ratios of monomer (aniline), oxidant (ammonium peroxydisulfate), and dopant (hydrochloric acid) on the polymerization of polyaniline (PANI) were investigated using direct ultrasonic irradiation technique. The effects of varying molar ratio of dopant and oxidant on the structural stability, morphology, and electrical conductivity of the prepared PANI were studied. Firstly, a scheme derived from electrical conductivity point of view, by varying the molar ratio of ammonium peroxydisulfate (APS). As the molar ratio of APS to aniline (ANI) varied from 0.1 to 1.25, the conductivity of PANI reached a maximum of 0.24 S/cm at a ratio of 1. Thereafter, by fixing the optimized molar ratio of APS and aniline the molar ratio of hydrochloric acid (HCl) was varied. The conductivity of PANI increased with an increase of HCl concentration and reached a maximum of 0.5 S/cm at an HCl concentration of 2 M. Finally, the formation mechanism for polymerization of PANI were discussed using Fourier transform infrared spectra, ultraviolet–visible spectra, nuclear magnetic resonance spectroscopy, and X-ray diffraction spectroscopy. The final product is in protonated form, possessing structural stability and electrically conductive.     

Optimization of the conductivity and yield of chemically synthesized polyaniline using a design of experiments

The electrical conductivity and yield of polyaniline (PANi) were optimized using a design of experiments (DOE). PANi samples were synthesized by the chemical oxidative polymerization of aniline using methane sulfonic acid as the dopant acid and ammonium persulfate as the oxidant. The main factors in the synthesis of PANi that can affect the conductivity were identified as (i) the concentration of dopant acid, (ii) oxidant‐to‐monomer ratio, and (iii) the addition rate of oxidant to monomer. Using a Box‐Behnken DOE method the regression equation, main effects plots, contour plots, and optimization plots for conductivity and yield were generated and analyzed. Under the optimized conditions of dopant acid concentration of 0.9M, an oxidant addition rate of 30 mL/h and an OM ratio of 0.9, PANi with a conductivity of 1.95 S/cm and yield of 95% was obtained. The observed trends in the four‐point probe conductivity measurements were correlated with the polymer structure using fourier transform infrared spectroscopy, X‐ray diffraction studies, and scanning electron microscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1047‐1057, 2013     

Synthetic process engineered polyaniline nanostructures with tunable morphology and physical properties

Polyaniline (PANI) nanofibers (NFs) obtained by the interfacial polymerization method are studied and compared with PANI nanostructures prepared by the ultrasonication method and the polymer acid doping method. In the case of PANI NFs, the effects of the reaction time, the size of the interfacial area, scale ratio, and concentration of reactant on the crystalline structure, thermal stability, morphology, electrical conductivity and dielectric permittivity are systematically studied. Meanwhile, huge difference in morphology is observed and related to the nanofiber growth condition. Unusual morphology and peaks on X-ray diffraction curve of PANI doped with polymer acid (poly(2-acrylamido-2-methyl-1-propanesulfonic acid)) (PAMPSA) are observed and associated with high molecular weight of the doped polymer acid. The change of the conductivity is attributed to a combination of crystallinity and crystal size. Temperature dependent conductivity reveals a 3-d variable range hopping (VRH) electron transport mechanism. The electrical conductivity and dielectric permittivity are investigated and mainly depend on the morphology and crystalline structure. The resistivity of the PANI NFs is observed to be the lowest one compared with the other two at room temperature. Both PANI nanostructures (NFs and NPs) exhibit negative real permittivity in the whole frequency range. Meanwhile, positive magnetoresistance (MR) is observed in all the three kinds of PANI nanostructures and is analyzed theoretically from the currently available wave-function shrinkage model.     

Dielectric Behavior of Lead-Silicate Glasses Containing Iron

The ac conductivity of lead-silicate glasses containing Fe was measured in the range 4.5° to 500° K to investigate the electronic hopping mechanism in these amorphous materials. Classes containing 0.0, 2.0, and 10.0 wt% Fe₂O₂ were prepared under normal atmospheric conditions. The ac conductivity, which increased with increasing Fe concentration, followed an Arrhenius expression at the higher temperatures. The activation energy for ac conduction increased with increasing Fe concentration, in contrast to the usual decrease in activation energy observed by other workers. The frequency of the conductivity σ (ω) was approximately of the form σ (ω)αω^-n where the exponent increases with increasing Fe concentration and temperature. This behavior is explained by assuming that a distribution of hopping distances and activation energies is involved in the ac electron transport mechanism. At low temperatures, the curves for tanδ vs T for all samples showed a broad relaxation peak at ∼ 70°K. Although this peak is frequency-dependent, it was independent of Fe concentration. The results did not indicate electron hopping between localized states in the temperature range studied.     

Structural and optical properties of self-assembled polypyrrole nanotubes

Polypyrrole (PPy) nanotubes doped with camphorsulfonic acid (CSA) have been synthesized using self-assembly polymerization method. The average diameter of the resulting PPy nanotubes has been controlled by varying the dopant/monomer molar ratio. Formation mechanism of PPy nanotubes has been discussed at length. The formation of PPy nanotubes has been confirmed from the high resolution transmission electron microscopy (HRTEM) studies. FTIR studies depict that the “effective conjugation length” of PPy nanotubes increases with increasing CSA/Py molar ratio. UV-vis studies reveal the formation of polaron and bipolaron bands within the band gap of neural PPy, confirming the doping of PPy nanotubes with CSA. The optical band gap energy decreases with increasing CSA/Py ratio and also the thermal stability of PPy nanotubes gets enhanced with increasing dopant/monomer molar ratio.     

Direct‐current conductivity at a cryogenically low temperature for polymer/carbon composites: Applicability of different theoretical models

In this study, we focused on the behavior of the direct‐current (dc) conductivity/resistivity in a cryogenically low temperature region (10–300 K) for ethylene vinyl acetate copolymer, acrylonitrile butadiene copolymer, and their 50/50 blend composites filled with different conductive carbons. The composites were prepared through a melt‐mixing technique. Different behaviors of the dc resistivity/relative resistivity for the composites were observed; these behaviors depended on the nature of the polymers, the filler types, and the filler concentration when plotted with respect to the temperature. The results of dc conductivity were fitted with some existing theoretical models, including Arrhenius, Kivelson, and Mott's variable range hopping, to check their applicability for these composite systems. We observed that none of the models was applicable within the entire range of measurement temperatures but were confined within limited temperature ranges. The reason behind the nonapplicability of the models is discussed with consideration of their drawbacks and limitations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43541.     

Photoluminescence,FTIR, and electrical characterization of samarium(III) chloride‐doped polyaniline

The synthesized polyaniline (PANI) is doped with different concentrations of Samarium(III) chloride (SmCl₃). The electrical conductivity of doped PANI samples has been measured in the temperature range (300–400K). It has been found that dc conductivity increases with the increase of dopant concentration. Different parameters, based on the conductivity, such as pre‐exponential factor (σ₀) and activation energy (ΔE) have also been calculated. These parameters exhibit information about the nature and suitability of the dopant. Doped samples are characterized by FTIR and photoluminescence studies, which show the interaction of dopant with PANI. Two sharp peaks of different intensities from PL spectra at 388 and 604nm have appeared in doped PANI, which might be due to the effect of SmCl₃. It has been observed that SmCl₃ (dopant) shows noticeable changes in the electrical and spectroscopic properties of doped PANI. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of ultrasonic assisted processing and clay nanofiller on dielectric properties and lithium ion transport mechanism of poly(methyl methacrylate) based plasticized polymer electrolytes

Lithium ion conducting solid polymer electrolyte (SPE) films consisted of poly(methyl methacrylate) (PMMA) matrix with lithium perchlorate as a dopant ionic salt, poly(ethylene glycol) as plasticizer and montmorillonite clay as inorganic nanofiller have been prepared by classical solution casting and high intensity ultrasonic assisted solution casting methods. The X‐ray diffraction study confirmed the amorphous structure of all these PMMA‐based solid electrolytes and the clay nanosheets existed in exfoliated form in their amorphous phase. Dielectric relaxation spectroscopy had been employed for the investigation of complex dielectric function, ac electrical conductivity, electric modulus, and impedance spectra of these electrolytes over the frequency range from 20 Hz to 1 MHz. It was observed that the dielectric properties and ionic conductivity of the electrolytes strongly depended on the sample preparation methods, and also had changes with addition of the clay nanofiller. Temperature‐dependent dielectric study of the electrolyte films confirmed that their dc ionic conductivity and conductivity relaxation time values obeyed the Arrhenius behavior. This study also revealed that the lithium ion transportation in the ion–dipolar complexes of these electrolytes occurred through hopping mechanism and it was correlated with the conductivity relaxation time. Preparation of these electrolyte films through ultrasonic assisted solution casting method increased the ionic conductivity by more than one order of magnitude in comparison to that of the classical solution casting method, which revealed that the former was a novel method for the preparation of these SPEs of relatively enhanced ionic conductivity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42188.     

Electron transport in Fe-doped polyvinyl acetate films

The electrical conductivity and current-voltage characteristics of pure and Fe³⁺-doped polyvinyl acetate films have been studied for various temperatures and bias field strengths. The activation energy for conduction showed an increasing trend with increasing dopant concentration. This has been attributed to the formation of molecular aggregates. The variation of electrical conductivity for doped films with temperature showed three regions with different activation energies. This behaviour has been explained in terms of the type of conduction mechanism operating in the material. It has been suggested that at low temperatures the conduction is electronic while at high temperatures it appears to be ionic. As the dopant concentration increases ionic conduction tends to dominate the electronic conduction even at low temperatures. From the current-voltage measurements it has been concluded that the conduction mechanism tends towards Schottky type with increasing dopant concentration.     

Electrochemical synthesis of nanostructured polyaniline: Heat treatment and synergistic effect of simultaneous dual doping

Different nanostructured polyaniline (PAni) has been synthesized via facile template‐free electrochemical synthesis approach in aqueous medium. Instead of conventionally used aniline, aniline sulphate was used in electrochemical polymerization. The synthesis process involves simultaneous doping with combination of inorganic and organic acid, i.e., sulfuric acid (H₂SO₄) and p‐toluenesulfonic acid (PTSA) at different ratios keeping total dopant concentration constant. Synergistic increase in conductivity is observed and the best conductivity is achieved at 3:1 ratio of [H₂SO₄]:[PTSA]. Different nanostructures of PAni are revealed through morphological analysis consisting of nanosphere, nanorod, and clustered particles among which finer nanorods show the best electrical conductivity. Upon controlled heat treatment followed by further cooling, resistivity increases, but after one day it decreases again and in the optimized dual doped PAni, it approaches approximately the same value of initial resistance. Lattice strain and benzenoid to quinonoid ratio increases with heat treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Anomalous electrical transport properties of PVA–Ag composite films below room temperature

The direct current (dc) and alternate current (ac) electrical transport property of polyvinyl alcohol–silver (PVA–Ag) composites has been investigated within a temperature range of 77 ≤ T ≤ 300 K and in the frequency range of 20 Hz to 1 MHz in the presence as well as in the absence of a transverse magnetic field up to 1 T. The dc conductivity follows variable range hopping model. The magnetoconductivity of the samples undergoes a change from negative to positive values with the incorporation of Ag in PVA matrix, which can be interpreted by the dominancy of the forward interference effect prevailing over the wave function shrinkage effect. The ac conductivity follows a power law of frequency, whereas the temperature dependence of frequency exponent “s” can be explained by correlated barrier hopping model. The dielectric behavior of the samples has been governed by the grain and interfacial grain boundary resistance and capacitance. Two activation behaviors are observed from the analysis of grain and interfacial grain boundary contributions. POLYM. COMPOS., 33:1941–1950, 2012. © 2012 Society of Plastics Engineers     

Synergistic effect of dopant combination and switchover in formation mechanism of polyaniline nanowire

Self‐assembled polyaniline (PAni) was synthesized electrochemically in dimethylformamide medium to study the effect of simultaneous use of organic–inorganic dopant combination in aprotic polar synthesis medium. During the synthesis process, simultaneous dual doping was performed using p‐toluenesulfonic acid and sulfuric acid with varying the ratio of the dopants keeping their total concentration unchanged. Nanowire meshes were formed where switchover in nanostructure formation is observed. Nanowire in individually doped PAni was formed with directional joining of smaller nanoparticles or from multilayered tubular nanostructures whereas, for dual doped PAni, either of these two was observed. Periodicity parallel and perpendicular to polymer chain were found in well correlation with diameter of nanowires. Synergistic improvements in AC conductivity, specific capacitance, and thermal degradation within certain temperature range were observed in particular ratio of the dopants. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41520.     

Studies on Fourier transform infrared spectroscopy,scanning electron microscope,and direct current conductivity of polyaniline doped zinc ferrite

In situ polymerization of aniline was carried out in the presence of zinc ferrite to synthesize polyaniline/ZnFe₂O₄ composites (PANI/ZnFe₂O₄) by chemical oxidation method. The composites have been synthesized with various compositions (10, 20, 30, 40, and 50 wt %) of zinc ferrite in PANI. From the Fourier transform infrared spectroscopy (FTIR) studies on polyaniline/ZnFe₂O₄ composites, the peak at 1140 cm⁻¹ is considered to be measure of the degree of electron delocalization. The surface morphology of these composites was studied with scanning electron micrograph (SEM). The dc conductivity has been studied in the temperature range from 40–160°C and supports the one‐dimensional variable range hopping (1DVRH) model proposed by Mott. The results obtained for these composites are of scientific and technological interest. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evolution in the Electronic Structure of Polymer‐derived Amorphous Silicon Carbide

The electronic structure of polymer‐derived amorphous silicon carbide pyrolyzed at different temperatures was investigated by combining measurements of their temperature‐dependent conductivity and optical absorption. By comparing the experimental results with theoretical models, the parameters such as conduction band, band‐tail, defect energy, and Fermi energy were determined. The results revealed that band gap and band‐tail width decreased with increasing pyrolysis temperature. Furthermore, it was found that electrons transport followed a band‐tail hopping mechanism, rather than variable range hopping. These results were discussed in accordance with the microstructural evolutions of the material.     

Spectroscopic,electrical, and relaxor‐like properties of cellulose acetate–erbium (III) chloride composite films

Cellulose acetate thin films doped with erbium (III) chloride (ErCl₃) of different concentrations were prepared by the solution method. The prepared composite films were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis. IR spectral analysis, UV–visible absorption, a.c. conductivity, and dielectric properties were investigated. The studied ErCl₃‐doped samples showed different properties from those of their pure components. SEM micrographs showed that for small dopant concentrations, samples tend to form conducting nanostructures with negligible particle agglomeration. DSC showed a monotonic development of the glass transition temperature by increasing the concentration of dopant material. Variation in the height, shape, and position of the bands in infrared transmission spectra, as well as the glass transition temperatures, indicated a complex interaction with the polymer molecular chains. Thermal stability and thermodynamic parameters were found to be concentration dependent. The electronic transitions’ band gabs and energy tails were calculated from the optical data. The dielectric studies showed that the correlated barrier hopping model was the dominant mechanism of a.c. conductivity. We found that samples with 10% and 20% ErCl₃ exhibited high dielectric constants and have pronounced electrostriction and relaxor‐like properties. Such samples can be used in many applications like electromechanical and thermomechanical transducers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45220.     

Synthesis and properties of soluble polypyrrole doped with dodecylbenzenesulfonate and combined with polymeric additive poly(ethylene glycol)

Soluble polypyrrole (PPy) samples advanced in electrical conductivity σ were chemically synthesized with dodecylbenzenesulfonate (DBS) sodium salt as a dopant, with poly(ethylene glycol) (PEG) as an additive, and with ammonium persulfate as an oxidant. The PPy–DBS–PEG samples were soluble in organic solvents (N‐methylpyrrolinone and m‐cresol). The greater the molar percentage ratio was of DBS, the greater the solubility was of synthesized PPy composites (PPy–DBS–PEG). The maximum electrical conductivity at room temperature for PPy–DBS–PEG was 1.02 S/cm, which was in fact the true conductivity of 100/10 (mol %) PPy/DBS. The chemical composition and doping level of PPy–DBS–PEG were determined by elemental analysis. The results of Fourier transform infrared spectroscopy were used for the structural characterization of PPy–DBS–PEG. The scanning electron microscopy results showed that the electrical conductivity was related to the morphology of PPy–DBS–PEG. According to thermogravimetric analysis, PPy–DBS–PEG was more thermostable than PPy–DBS. Electron spin resonance measurements showed that the polaron and bipolaron acted as charge carriers of PPy–DBS–PEG. According to the temperature dependence of the electrical conductivity, PPy–DBS–PEG was a semiconductor and followed the three‐dimensional variable‐range hopping model. The improved electrical conductivity apparently resulted from the reduction of the crosslinking and structural defects of the PPy chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1170–1175, 2005     

Charge transport mechanism in intercalated polypyrrole aluminum‐pillared montmorillonite clay nanocomposites

Nanocomposites based on intercalated conducting polypyrrole (PPy) into the galleries of inorganic aluminum‐pillared Montmorillonite (Al‐PMMT) clay with varying concentrations of Al‐PMMT were prepared by in situ chemical polymerization. The intercalation was confirmed by X‐ray diffraction pattern. Charge transport mechanism in these composites was investigated by temperature dependent direct current conductivity measurements. An increase in DC conductivity value on addition of (Al‐PMMT) clay in the composites at all temperatures and a transition from three‐dimensional (3D) Mott's variable range hopping (VRH) process in pristine PPy to one‐dimensional (1D) Mott's VRH process in the intercalated polymer composites has been observed. This transition in charge transport mechanism of PPy from 3D VRH to 1D VRH on intercalation has been interpreted in terms of straightening and linearization of polymer chains and decrease in inter‐chain interactions in the intercalated PPy. Enhancement in mechanical properties and increase in thermal stability of the nanocomposites was also observed with the increase in weight percentage of Al‐PMMT in PPy‐Al‐PMMT composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012