Dielectric behavior and charge transport in polyaniline nanofiber reinforced PMMA composites

PAni nanofibers synthesized by interfacial polymerization were reinforced in the PMMA matrix in different weight ratios. Randomly oriented polyaniline nanofibers were observed in the TEM image with diameter ranging from 20 to 30 nm. The SEM revealed the microstructure of the fiber reinforced composites showing better connectivity. The XRD spectra of the composites showed peaks at 2θ=17.05°, 20.3°, 27.15° and 30.05° that were indexed in a pseudo-orthorhombic unit cell. The dielectric constant measured over a frequency range of 42 Hz-1 MHz and in the temperature range of 303-373 K showed dependence upon frequency, temperature and concentration of the conducting nanofibers in the composites. The ac conductivity (σ_ac) was interpreted as a power law of frequency. The frequency exponent s was found to lie in the range from 0.4 to 0.65 and decreased with the increase in temperature, which suggested that correlated barrier hopping (CBH) was the dominant charge transport mechanism. Existence of polarons as major charge carriers was confirmed by the low values of polaron binding energy (W_M). Decrease in the values of density of states N(E_F) with the increase in PAni nanofiber concentration indicated increased delocalization of electronic states in the band gap causing the increase in ac conductivity.     

Electrical,thermal and spectroscopic studies of Te doped polyaniline

In the present paper, we have reported the chemical synthesis and characterization of polyaniline doped with tellurium. The aniline was polymerized by chemical oxidation using ammonium persulphate as an oxidant and was doped with different concentrations of tellurium. Doped PANI was characterized by using FTIR, DSC and two-probe conductivity measurement. The dc conductivity has been measured to see the effect of tellurium and its mechanism has been explained by the formation of polarons and bipolarons that move along the polymer chain, and gives rise to the electrical conductivity. The observed increase in conductivity of polyaniline is attributed due to the incorporation of Te into the PANI chain. Glass transition temperature (T_g) and enthalpy (ΔH) have been calculated from DSC measurements. FTIR spectra suggest the structural changes after incorporation of Te in polymeric chain.     

Dielectric properties and EMI shielding efficiency of polyaniline and ethylene 1-octene based semi-conducting composites

The preparation of polyaniline (PAni) was carried out by the oxidative emulsion polymerization of aniline and the semi-conducting composites were prepared by mixing it with a polyolefinic thermoplastic elastomer ethylene 1-octene copolymer (EN). Different electrical properties and electromagnetic interference shielding efficiency (EMI SE) of these composites were measured. The results revealed that the incorporation of PAni in EN increases the conductivity, dielectric constant, dielectric loss and EMI SE. These composites exhibit pressure dependent dielectric properties and may act as pressure sensor. There are increase in AC conductivity and decrease in dielectric constant with the increase in applied pressure on composites. A model correlation between EMI SE and AC conductivity at same frequency for the composites having maximum 40% of PAni was obtained through extrapolation and linear regression analysis, which shows that EMI SE has linear relationship with AC conductivity. Because of their semi-conductive behavior these composites can find application as antistatic materials and electromagnetic interference (EMI) shielding material.     

Dielectric and electro-optical studies of a nickel-ferrite-nanoparticle- doped ferroelectric liquid crystal mixture

Effect of magnetic nanoparticles (nickel ferrite) doping on the dielectric and electro-optical properties of a ferroelectric liquid crystal mixture has been studied. In a doped ferroelectric liquid crystal mixture, dispersion of a small amount (0.25 wt.%) of nickel ferrite nanoparticles decreases the polarization and improves the response time compared to an undoped mixture. The significant changes in the polarization and response time are explained on the basis of dipole–dipole interaction and anchoring phenomena. Dielectric permittivity also increases with increasing the temperature of the SmC* phase and shows a reduction in dielectric loss in a doped sample. A Goldstone mode is clearly observed at ～200 and ～500 Hz in an undoped and a doped sample, respectively.     

Positron beam studies on polyaniline and Ag-coated polyaniline

The effect of doping of the polyaniline emeraldine base (PEB), with Ni as well as Ni over layer coating has been investigated using variable low energy positron beam. Depth-resolved Doppler S-parameter measurements have been performed on undoped, Ni-doped polyaniline (PANI), and Ag (40 nm) film deposited PANI samples. Significant variation in S-parameter is observed for undoped and Ni-doped PANI. The size of the free volume hole has shifted to lower values upon doping with Ni as compared to that of undoped PANI, which is consistent with the conductivity measurements. For Ag-coated PANI systems, the S vs. E_p curves show distinct changes at the surface and interior regions. These results are discussed in the light of changes in free volume hole size distribution.     

AC impedance analysis of polyaniline–montmorillonite nanocomposites

Investigation of the electrical properties of polymer–clay nanocomposites is important in the development of nanoelectronic devices. These nanocomposites may be prepared by intercalating suitable monomers within interlayer spaces of expanding layered clay materials, followed by in situ polymerization. We made use of this approach to prepare montmorillonite–polyaniline nanocomposites by ion-exchanging the intergallery cations for anilinium ions and subsequently polymerizing the anilinium ions by peroxydisulphate in the acidic medium to yield emeraldine salt form of polyaniline intercalated in montmorillonite (ES1-MMT). The emeraldine salt form of polyaniline contains one positive charge per three monomer units, and hence, polymerization of anilinium ions reduces the number of cations present within the interlayer. Charge compensation thus requires uptake of required amount of cations from the solution. Further, the emeraldine salt form of polyaniline can be neutralized by treating with excess base such as ammonia. Thus, the neutralization of emeraldine salt results in an uptake of ammonium ions for charge balance. We have, therefore, neutralized ES1-MMT using aqueous ammonium hydroxide, and the cations inserted into the interlayer were again exchanged for anilinium ions. The latter was polymerized in acidic medium to yield more polyaniline in its emeraldine salt form (ES2-MMT). By repeating this procedure we have also prepared ES3-MMT. X-ray diffraction (XRD) spectra recorded at 150 °C reveal the enhancement of d-spacing upon increased amounts of polymer formation, and the Fourier transform infrared (FTIR) analysis also supports this by showing enhanced absorption due to bands typical of emeraldine salt (for example, B–NH⁺ = Q, where B and Q stand for benzanoid and quinoid, respectively). Careful analyses of FTIR spectra reveal that the polymer is present within the interlayers, as well as adsorbed onto the external surfaces and is bound to clay layers through hydrogen bonding. In this publication, we report the electrical properties of such ES-MMT nanocomposites. Alternating current (AC) impedance analysis shows that the nanocomposites are highly conducting materials, and their bulk conductivity enhances in the order ES1-MMT < ES2-MMT < ES3-MMT. The materials are pure electronic conductors as revealed by the direct current polarization studies. Further, their conductivities decrease with increasing temperature as of pure electronic conductors. By treating kaolinite with anilinium ions in acidic medium followed by peroxydisulphate ions, emeraldine salt–kaolinite (ES-KAL) composites have also been prepared. Because kaolinite is a non-expanding clay, the ion exchange is not possible, and hence, the polymer cannot be incorporated into the interlayer. This is indeed shown in the XRD analysis. The polymer can only reside out of the kaolinite particles. FTIR spectra reveal the hydrogen bonding between the polymer and kaolinite outer surfaces. AC impedance spectra of ES-KAL do not show high bulk conductivity. Thus, the comparison of AC impedance spectra of ES-KAL with ES-MMT systems clearly indicates that the bulk conductivity of the latter systems is predominantly due to intercalated polyaniline.     

Dielectric response in novel polyvinylidene fluoride/nanoquasicrystalline composites

The dielectric behavior of polyvinylidene fluoride/nanoquasicrystalline Al–Cu–Fe composites has been investigated over a broad frequency range. High effective dielectric constant (3800) at 100 Hz is observed near the percolation threshold. The dielectric behavior has been explained on the basis of boundary layer capacitor effect, Maxwell Wagner Sillars interfacial polarization and percolation theory while the dielectric anomalies are attributed to process of fabrication leading to thick insulating layer between the filler particles forming a gap in effective tunneling range of two filler particles, inhibiting the probability of higher order tunneling. The mechanical/electronic properties of these composites will make them suitable for multifunctional applications.     

Synthesis,characterization and electrochemical impedance spectroscopy of VOx-NTs/PPy composites

Composites consisting of vanadium oxide nanotubes (VOx-NTs) and polypyrrole (PPy) were synthesized by a two-steps method. VOx-NTs were firstly prepared by a combined sol–gel reaction and hydrothermal treatment procedure, in which V ₂O₅ powder and H₂O₂ were used as raw materials and hexadecylamine as a structure-directing template. Then VOx-NTs/PPy composites were fabricated by a cationic exchange reaction between hexadecylamine and polypyrrole. The structure and morphology of the samples were investigated by SEM, TEM, XRD and FTIR techniques. The results confirmed that the template molecules were successfully substituted by the conducting polymers PPy without destroying the previous tubular structure. Electrochemical impedance spectroscopy (EIS) measurements were performed to evaluate the electrochemical kinetics of the samples. The results indicated that VOx-NTs/PPy composites had a lower charge transfer resistance and a faster lithium-ion diffusion speed than those of VOx-NTs, and the enhanced electrochemical kinetics could be attributed to the excellent electronic conductivity of polypyrrole.     

Electrical conductivity and dielectric properties of sulfamic acid doped polyaniline

The temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) is studied for different samples of polyaniline (PANI), doped with different concentration of sulfamic acid in the frequency range (10–100 kHz) and temperature range (300–400 K). The dc conductivity has also been measured to see the effect of sulfamic acid and the conduction mechanism has been explained by the propagation of polaron through a conjugated polymer chain due to shifting of double bonds (alternation), which gives rise to electrical conduction.     

Preparation of highly conductive CNTs/polyaniline composites through plasma pretreating and in-situ polymerization

In this study, carbon nanotubes (CNTs) were pretreated by plasma, and further in-situ polymerized with aniline to achieve uniform CNTs/polyaniline (PANI) composites with high conductivity. The highest conductivity (2.946 S/cm) of CNTs/PANI composites under optimum plasma treating parameters is much higher than those without CNTs pretreatment or premodified by acid oxidation method. The scanning electronic microscope (SEM) pictures indicate that smooth surfaces of pristine CNTs (diameter: 20-40 nm) changes into rough structures and the size increases to around 90 nm, which is further proved by the X-ray diffraction (XRD), the Fourier transform infrared spectroscopy (FTIR), and the Raman measurements. Thermogravimetric analysis (TGA) results reveal that the thermal stability of CNTs/PANI composite is better than that of pure PANI.     

Synthesis and electrochemical properties of three-dimensional graphene/polyaniline composites for supercapacitor electrode materials

To improve the specific capacitance and rate capability of electrode material for supercapacitors, a three-dimensional graphene/polyaniline(3DGN/PANI) composite is prepared via in situ polymerization on GN hydrogel. PANI grows on the GN surface as a thin film, and its content in the composite is controlled by the concentration of the reaction monomer. The specific capacitance of the 3DGN/PANI composite containing 10 wt% PANI reaches 322.8 F·g-1at a current density of1 A·g-1, nearly twice as large as that of the pure 3DGN(162.8 F·g-1). The capacitance of the composite is 307.9 F·g-1at 30 A·g-1(maintaining 95.4%), and 89% retention after 500 cycles. This study demonstrates the exciting potential of3DGN/PANI with high capacitance, excellent rate capability and long cycling life for supercapacitors.     

Tubular composite of doped polyaniline with multi-walled carbon nanotubes

We report on the synthesis of tubular composite of doped polyaniline (PANI) with carboxylic groups contained multi-walled carbon nanotube (MWNTs) by in situ polymerization. Based on the interaction between aniline monomers and c-MWNTs , aniline molecules were adsorbed and polymerized on the surface of c-MWNTs . The structural characterization showed that tubular composites are core (c-MWNTs )-shell (doped-PANI) structures with diameters of several tens of nanometers, and lengths of up to several hundreds of nanometers. The conductivities of these tubular composites are several times higher than that of PANI without MWNT, which will offer new application possibilities. PACS 81.05.Qk; 81.05.Tp     

Dielectric relaxation of KBr doped with KOH and KOD

The complex dielectric constant of KBr single crystals doped with KOH and with KOD has been measured in the temperature range from 0.32°K to 300°K using a small a. c. signal. A relaxation timeτ ₀ was determined by means of Cole-Cole plots. ForT<4°K the temperature dependence ofτ ₀ can be approximated byAT ^?n , wheren is between 1.2 and 1.3 for the dilute samples, and between 0.8 and 1.0 for two samples with large hydroxyl concentrations.n has the same value for OH^? and OD^? dipoles. The constantA roughly doubles upon substitution ofH byD. The relaxation behavior was found to be independent of concentration in the range between 3×10¹⁸ cm^?3 dipoles and 10¹⁹ dipoles cm^?3.     

Dielectric and optical properties of gadolinium doped bismuth ferrite

Polycrystalline samples of a Gd _x Bi_1?x FeO₃ system are prepared by a conventional ceramic technology. Temperature and frequency dependences of a component of permittivity in the range of radio- and ultra-high frequencies are investigated. Features of the behavior of the reflectance spectra and spectra of the components of the dielectric and optical functions in the region of lattice and electronic resonances are investigated.     

Dielectric study of polyaniline/poly (methylmethacrylate) composite films below the percolation threshold

We report results of dielectric relaxation studies of polyaniline/poly(methylmethacrylate) composites with polyaniline amount less than the percolation threshold in the frequency range of 0.1 Hz to 1 MHz and temperature range of 10 °C–170 °C. We find a significant dependence of the glass transition temperature Tg on the polyaniline amount in the composite. α and β relaxation processes relative to the PMMA matrix are also affected by the presence of polyaniline inclusion. We identify a relaxation process due to ionic conductivity and another process attributed to residual solvent. The characteristic relaxation frequency of each process and the activation energy depend on the polyaniline amount in the composite. The ac conductivity in the high frequency range is fitted to the universal power law of Jonscher characteristic of disordered materials.     

纳米管结构聚苯胺的电阻率和磁化率

研究了用自组装法制备的质子酸掺杂的纳米管结构聚苯胺的电阻率(ρ)和磁化率随温度变化的依赖关系，讨论了质子酸掺杂浓度、不同对阴离子以及苯胺单体与质子酸聚合时反应浓度对纳米管结构聚苯胺电学性质的影响.实验结果表明，lnρ和T-1/2呈线性关系，不同对阴离子对聚苯胺的电阻率影响很大，随着质子酸掺杂浓度以及苯胺单体与质子酸聚合时反应浓度的增大，聚苯胺的电阻率明显减小；而且，其磁化率可以表示为与温度无关的泡利顺磁性和符合居里定律的顺磁性之和.     

Dielectric and magnetic properties of low-temperature fired NiCuZn-BaTiO3 composites

The composition effects on the dielectric and magnetic properties of NiCuZn-BaTiO₃ composites fired at low temperature were investigated. The coexistence of perovskite BaTiO₃ and spinel ferrite phases in the composites were observed; no significant chemical reactions occurred between BaTiO₃ and NiCuZn ceramics during sintering. The nanosized BaTiO₃ powders favored a decrease in grain size. The saturation magnetization, remanent magnetization and real permeability continuously decreased with increasing BaTiO₃ content. And the real permittivity continuously increased with the BaTiO₃ content. The Q-factor (quality factor) exhibited relatively high values with 20-30 wt% BaTiO₃. All composite materials exhibited a low dielectric loss below 100 MHz. Synthetically considerations, the composites with 20-30 wt% BaTiO₃ could obtain relatively high real permeability and real permittivity values, and the magnetic and dielectric losses were relatively low, so they were the best candidates to produce LC-integrated chip elements.     

Dielectric properties of ferroelectric/DMS heterointerface using YMnO3 and Ce doped Si

Bottom gate type Al/Si:8.2 at%Ce/YMnO₃/Pt capacitor was fabricated. Although it was polycrystalline, we successfully obtained Si:8.2 at%Ce film on ferroelectric YMnO₃. The dielectric properties of the capacitor were carefully investigated. Although the capacitance shows frequency dispersion, the capacitor exhibits a ferroelectric type C-V hysteresis loop. From the PUND and P-V measurements, ferroelectric polarization was distinguished from the another polarization, Based on these dielectric measurements, effect of polarization induced by the ferroelectric YMnO₃ on the carrier modulation in the diluted magnetic semiconductor, Ce doped Si film was discussed.     

Role of mesoscopic morphology in charge transport of doped polyaniline

In doped polyaniline (PANI), the charge transport properties are determined by mesoscopic morphology, which in turn is controlled by the molecular recognition interactions among polymer chain, dopant and solvent, Molecular recognition plays a significant role in chain conformation and charge delocalization. The resistivity of PANI doped by camphor sulfonic acid (CSA)/2-acrylo-amido-1-propane sulfonic acid (AMPSA)/dodecyl benzene sulfonic acid (DBSA) is around 0.02 Ω cm. PANI-CSA and PANI-AMPSA show a metallic positive temperature coefficient of resistivity above 150 K. with a finite value of conductivity at 1.4 K; whereas, PANI-DBSA shows hopping transport at low temperatures. The magnetoresistance is positive (negative) for PANI-CSA (PANI-AMPSA); and PANI-DBSA has a large positive MR. The behavior of MR suggests subtle variations in mesoscopic morphology between PANI-CSA and PANI-AMPSA.