Effect of dopant type on the properties of polyaniline

The comparative study on the effect of different type of dopants on the properties of polyaniline (PANI) is relative less although dopant has profound effect of the properties of PANI. So, the aim of the present work is to study the effect of different type of dopant, namely strong inorganic hydrochloric acid (HCl), organic and aromatic acids containing different aromatic substitution, namely p‐toluene sulfonic acid (PTSA), dodecylbenzenesulfonic acid (DBSA), organic and aliphatic acids having long hydrocarbon chain, namely lauric acid (LA), on the properties of PANI. The PANI was prepared through oxidative polymerization methods and doped with HCl, PTSA, DBSA, and LA and then characterized through different methods like conductivity measurement, UV, X‐ray, DSC, TGA, and SEM. It was found that the properties of doped PANI depend on the type and molecular size of the dopant. With the increase in dopant chain length, the crystallinity is decreased, whereas the d‐spacing, interchain separation, and solubility are increased. The bond formation of water molecules with the backbone nitrogen of the polymers is much less in presence of aromatic dopants when compared with those of inorganic or aliphatic dopants. All the doped polyanilines under investigation do not decompose up to 500°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal properties of processable polyaniline with novel sulfonic acid dopants

Thermal properties of melt processable polyaniline (PANI) synthesized by doping with functionalised novel sulfonic acid dopants have been investigated. Doping of PANI was carried out by using the dopants derived from an inexpensive naturally existing biomonomer, cardanol: sulfonic acid of 3‐pentadecylphenol, sulfonic acid of 3‐pentadecylanisole and sulfonic acid of 3‐pentadecylphenoxyacetic acid. These dopants act as very good plasticizing cum protonating agents for PANI. Doping was carried out either by mechanical mixing of emeraldine base and the dopant or by an in situ doping emulsion polymerization of aniline. Highly conducting free‐standing flexible films of protonated PANI could be prepared by a hot pressing method at different temperatures. The thermal stability and thermal reactions of these protonated PANI were followed by conductivity measurements at different temperatures, wide angle X‐ray diffraction measurements, thermogravimetric analysis and differential scanning colorimetry analysis. © 2001 Society of Chemical Industry     

Electromagnetic interference shielding behavior of polyaniline/graphite composites prepared by in situ emulsion pathway

Polyaniline–graphite composites were prepared via in situ emulsion pathway, using different weight ratios of aniline to graphite. These composites were characterized for thermal, electrical, and spectral attributes. The thermal stability (～ 230°C) and electrical conductivity (67.9 S/cm) were improved significantly as compared with polyaniline doped with conventional inorganic dopants such as HCl (140°C and 10 S/cm). Scanning electron micrographs indicated a systematic change in morphology from globular to flaky with increasing amounts of graphite. The relative shifting of UV–visible bands indicates that some interactions exist between doped polyaniline and graphite. Absorption‐dominated total electromagnetic interference shielding effectiveness of the order of ?33.6 dB suggests that these materials can be used as futuristic microwave shielding materials. The good electrical conductivity and thermal stability make them ideal candidates for preparing conducting composites by melt blending with conventional thermoplastics such as polyethylene, polypropylene, and polystyrene, etc. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A novel soluble PANI/TPU composite doped with inorganic and organic compound acid

A series of novel soluble and thermoplastic polyurethane/polyaniline (TPU/PANI) composites doped with a compound acid, which was composed of an organic acid (p‐toluene sulfonic acid) and an inorganic acid (phosphoric acid), were successfully prepared by in situ polymerization. The effect of aniline (ANI) content, ratio of organic acid/inorganic acid, and different preparation methods on the conductivity of the TPU/PANI composites were investigated by using conductivity measurement. Lithium bisoxalato borate (LiBOB) was added to the prepared in situ TPU/PANI to coordinate with the ether oxygen groups originating from the soft molecular chains of TPU, and thus the conductivity of the composites was further enhanced. The molecular structure, thermal properties, and morphology of the TPU/PANI composites were studied by UV–visible spectroscopy, differential scanning calorimetry, and scanning electron microscopy, respectively. The results show that the in situ TPU/PANI composites doped with the compound acid can be easily dissolved in normal solvents such as dimethylformamide (DMF) and 1,4‐dioxane. The conductivity of the TPU/PANI composites increases with the increase of the ANI content, in the ANI content range of 0–20 wt %; however, the conductivity of the composites reduces with further increment of ANI content. The conductivity of the TPU/PANI composites prepared by in situ polymerization is about two orders of magnitude higher than that prepared by solution blending method. LiBOB can endow the in situ TPU/PANI composites with an ionic conductivity. The dependence of the conductivity on temperature is in good accordance with the Arrhenius equation in the temperature range of 20–80°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on the dielectric properties of poly(o‐toluidine) and poly(o‐toluidine‐aniline) copolymer

Poly(o‐toluidine) (PoT) and poly(o‐toluidine co aniline) were prepared by using ammonium persulfate initiator, in the presence of 1M HCl. It was dried under different conditions: room temperature drying (48 h), oven drying (at 50°C for 12 h), or vacuum drying (under vacuum, at room temperature for 16 h). The dielectric properties, such as dielectric loss, conductivity, dielectric constant, dielectric heating coefficient, loss tangent, etc., were studied at microwave frequencies. A cavity perturbation technique was used for the study. The dielectric properties were found to be related to the frequency and drying conditions. Also, the copolymer showed better properties compared to PoT alone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 592–598, 2004     

Conducting polyaniline composites as microwave absorbers

Conducting polymers are excellent microwave absorbers and they show technological advantage when compared with inorganic electromagnetic absorbing materials, being light weight, easily processable, and the ability of changing the electromagnetic properties with nature and amount of dopants, synthesis conditions, etc. In this paper we report the synthesis, dielectric properties, and expected application of conducting composites based on polyaniline (PAN). Cyclohexanone soluble conducting PAN composites of microwave conductivity 12.5 S/m was synthesized by the in situ polymerization of aniline in the presence of emulsion grade polyvinyl chloride. The dielectric properties of the composites, especially the dielectric loss, conductivity, dielectric heating coefficient, absorption coefficient, and penetration depth, were studied using a HP8510 vector network analyzer. The microwave absorption of the composites were studied at different frequency bands i.e, S, C, and X bands (2–12 GHz). The absorption coefficient was found to be higher than 200 m⁻¹ and it can be used for making microwave absorbers in space applications. POLYM. COMPOS., 28:588–592, 2007. © 2007 Society of Plastics Engineers     

Synthesis and characterization of processable polyaniline doped with novel dopant NaSIPA

Aniline has been polymerized in the presence of a novel dopant sodio‐5‐sulfo‐isophthallic acid (NaSIPA), via the chemical oxidative polymerization route. The thermal stability and processability of polyaniline prepared by indirect method (PD1) have been improved significantly (290°C) as compared to polyaniline doped with conventional inorganic dopants like HCl or H₂SO₄, without much loss of electronic conductivity (5.07 S/cm in PD1). This suggests its use for melt blending with engineering thermoplastics. However, polyaniline prepared by direct method (PD2) can be melt‐blended only with conventional thermoplastics like polyethylene, polypropylene, polystyrene, etc. Low‐temperature studies reveal the 1‐D variable range hopping as a conduction mechanism for direct polymer (PD2), with parameters T_o and σ_o as 4112 K and 15.1 S/cm, respectively. However, for indirectly doped polymer (PD1) Arrhenius‐type model, having parameters |(E_F ? E_C)| and σ_C as 0.04 eV and 28.4 S/cm, respectively, it suited well. The coherence length as found from XRD data was around 28.8 nm for PD1 and 25.2 nm for PD2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase evolution and microwave dielectric properties of BaTi4O9 ceramics prepared by reaction sintering method

BaTi₄O₉ microwave dielectric ceramics were prepared by reaction sintering method using BaCO₃ and TiO₂ as raw materials. The phase evolution and the chemical reactions were proposed based on the X-ray diffraction results with sintering temperature. The microstructure characteristics were observed using scanning electron microscopy and energy dispersive spectrometer. The compact ceramics with a single phase of BaTi₄O₉ could be prepared successfully by reaction sintering method, exhibiting optimum microwave dielectric properties: a dielectric constant of 36.9, a high quality factor of 52 735 (at 7.5GHz), and a near zero temperature coefficient of resonant frequency of 5.8 ppm/°C, after sintering at 1200°C for 6 hours.     

Electrical,physicomechanical, and X‐ray studies on ethylene‐vinyl acetate copolymer/polyaniline blends

The conductive blend consisting of ethylene‐vinyl acetate (EVA) and a polyaniline/p‐toluene sulfonic acid (PAn/TSA) complex were prepared by a thermal doping process using a Brabender plasticorder at 150°C. The conductivity, dielectric constant, dissipation factor, mechanical behavior, and structural aspects of these blends were investigated. A higher percentage of the PAn/TSA complex in the EVA matrix resulted in an increase in the electrical properties and a decrease in the mechanical properties like the tensile strength and percentage of elongation. These results were compared with the microcrystalline parameters of the blend obtained from X‐ray profile analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1730–1735, 2002     

Shearing Effects on the Conducting Polymer Blends

To obtain a highly conductive polyblend based on doped polyaniline, an zinc salt based conductive master batch material (MB-13) made from mixing zinc n-dodecylbenzene sulfonate (Zn (DBS)₂) and n-dodecylbenzene sulfonic acid (HDBSA) polyaniline (PANI(DBSA)_0.5) together was compounded with PP in a melt-mixer varying the processing conditions. The SEM pictures show the morphologies of the polyblends were phase-separated into strips of elongated MB-13 for all samples. The elongation was first enhanced at shear rates ranged from 20 to 60 rpm. A shear rate of 60 rpm at 180 °C can elongate the conductive master batch phases (filler) to obtain both the highest aspect ratio and least resistance by keeping the secondary dopants of Zn (DBS)₂ stay within MB-13 from losing its conductivity and deformability.     

Temperature dependent dielectric properties of (na,K) NbO3, near equimolar composition

Pellet samples of Na_1-xK_xNbO₃ (0.490 ≤ x ≤ 0.510) were prepared using solid state reaction method with double sintering. Dielectric measurements were carried out on the prepared samples, from 30 to 500 °C, at 1 MHz. Dielectric constant and electrical conductivity were found minimum, for x = 0.500 among all the prepared compositions, at room temperature and at all the measured frequencies. Three distinguished phase transitions, at 200, 380 and 460 °C, were observed in dielectric measurements of the prepared compositions. The high temperature X-ray diffraction (HT- XRD) of the samples with x = 0.500, shows monoclinic phase between room temperature and 200 °C, tetragonal between 200 and 380 °C, tetragonal with increased lattice parameters, between 380 and 460 °C, and cubic phase beyond 460 °C. The tetragonal to tetragonal phase transition at 380 °C, and tetragonal to cubic at 460 °C was distinctly observed from dielectric and HT- XRD measurements in the present study.     

Microwave dielectric properties of low-temperature sinterable α-MoO3

The α-MoO₃ ceramics were prepared by uniaxial pressing and sintering of MoO₃ powder at 650 °C and their structure, microstructure, densification and sintering and microwave dielectric properties were investigated. The sintering temperature of α-MoO₃ was optimized based on the best densification and microwave dielectric properties. After sintering at 650 °C the relative permittivity was found to be 6.6 and the quality factor was 41,000 GHz at 11.3 GHz. The full-width half-maximum of the A_1g Raman mode of bulk α-MoO₃ at different sintering temperatures correlated well with the Qf values. Moreover, the sintered samples showed a temperature coefficient of the resonant frequency of ?25 ppm/°C in the temperature range from ?40 to 85 °C and they exhibited a very low coefficient of thermal expansion of ±4 ppm/°C. These microwave dielectric properties of α-MoO₃ will be of great benefit in future MoO₃ based materials and their applications.     

Properties evaluation of the membranes synthesized with castor oil polyurethane and polyaniline

Polymeric membranes for electrodialysis, fuel cells, and other purposes with specific characteristics have been the focus of innumerable researches. The aim of this work was to evaluate membranes of the sulfonated polyaniline and polyurethane, obtained in the presence of the former, regarding its mechanical and electrical properties. Polyurethane (PU) was prepared from castor oil and 4–4‐diciclohexilmethane isocyanate (HMDI). Polyaniline was synthesized by chemical oxidation, as described in the literature, and was sulfonated with chlorosulfonic acid in dichloroethane. Solution membranes were prepared by mixing sulfonated polyaniline (SPAN) and polyaniline doped with p‐toluene sulfonic acid (PAni_TSA) with castor oil and further HMDI. The obtained products were characterized by FTIR, TGA, and DMA. The membrane FTIR brought out the characteristic peaks of PU and polyanilines (TSA e sulfonated), and TGA curve showed a maximum decomposition rate at 350°C, quite different of the polyaniline ones. Nevertheless the SPAN/PU membrane showed very good stability until 250°C. The loss modulus curves show that there was an increase in the PU glass transition temperature with the addition of PAni and SPAN due to the their interaction with the PU chains. POLYM. ENG. SCI. 46:1485–1489, 2006. © 2006 Society of Plastics Engineers.     

The use of acrylated fatty acid methyl esters as styrene replacements in triglyceride‐based thermosetting polymers

Resins containing plant oil‐based cross‐linkers were studied with two reactive diluents: a styrene and an acrylated fatty acid methyl ester‐based (AFAME) monomer. Acrylated epoxidized soybean oil and maleinated castor oil monoglyceride were bio‐based cross‐linkers used. The viscosity and mechanical properties of the resulting polymers were measured and analyzed. Both bio‐based cross‐linkers prepared using the modified AFAME as diluent had a fairly high viscosity, so blends of AFAME and styrene were needed to meet the viscosity requirements established by the composite industry (<1000 cP at room temperature). In addition, the glass transition temperature (T_g) and stiffness of bio‐based cross‐linker/AFAME polymers were significantly lower than the resin/styrene polymers. Ternary blends of maleinated castor oil monoglyceride with AFAME and styrene improved the mechanical properties to acceptable comparable values (storage modulus at 30°C ～ 1200 MPa and T_g ～ 100°C). The addition of 5 wt% of chemically modified lignin led to an improvement in the mechanical properties of the polymeric matrix but caused an increase in the viscosity. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Microwave Dielectric Properties of Scheelite Structured PbMoO4 Ceramic with Ultralow Sintering Temperature

In this work, a low‐firing microwave dielectric ceramic PbMoO₄ with tetragonal structure was prepared via a solid‐state reaction method. The sintering temperature ranges from 570°C to 670°C. Ceramic samples with relative densities above 97% were obtained when sintering temperature was around 600°C. The best microwave dielectric properties were obtained in the ceramic sintered at 650°C for 2 h with a permittivity ~26.7, a Q × f value about 42 830 GHz (at 6.2 GHz) and a temperature coefficient value of 6.2 ppm/°C. From the X‐ray diffraction, backscattered electron imaging results of the cofired sample with 30 wt% silver and aluminum additive, the PbMoO₄ ceramic was found not to react with Ag and Al at 630°C. The microwave dielectric properties and low sintering temperature of PbMoO₄ ceramic make it a candidate for low‐temperature cofired ceramic applications.     

Effect of unsaturation in bicarboxylic acid dopants for solid‐state synthesis of polyaniline

Conjugation in the polymeric backbone leads to an electrical conducting nature for conducting polymers, and organic acids can be used as dopants to manipulate the electroactive behaviour. The present investigation deals with the effect of unsaturation in bicarboxylic acid dopant structures on the properties of polyaniline (PAni). PAni was synthesized via solvent‐free solid‐state polymerization. Oxalic acid, fumaric acid and trans,trans‐muconic acid containing 0, 1 and 2 double bonds, respectively, in their molecular structures were used as dopants. Fine particles directionally agglomerate to form nanowires. The use of a conjugated dopant results in highly crystalline PAni. With an increase in the number of double bonds in the dopant structure, the conductivity at room temperature increases, whereas the activation energy, hopping range, optical band gap and supercapacitive performance reduce. The inter‐chain hopping is expected to be favoured by the presence of unsaturation, and even more by conjugation in the dopant structure. © 2016 Society of Chemical Industry     

Investigation of dielectric properties of free standing electrospun nonwoven mat

Flexible materials with balanced dielectric as well as conductive characteristics have elucidated considerable demand in field of research where conventional dielectric or insulators can be replaced by recent advances in various electronics appliances. Our work describes the detailed analyses of dielectric properties like dielectric constant, losses, and electric modulus by means of broadband dielectric spectroscopy over frequency ranging from 0.1 Hz to 10 MHz and temperature ranging from 0 to 60 °C for poly(vinyl alcohol)‐polyaniline (PVA‐PANI) free standing electrospinning nonwoven mat. It has been contemplated that the dielectric constant was enhanced by increasing PANI concentration for complete range of frequency at room temperature. The enhanced dielectric constant value (5.14 at 0.1 Hz, 2.66 at 1 KHz, 2.58 at 10 KHz, and 2.19 at 10 MHz) was anticipated for 7 wt % loading of PANI which was attributed to the presence of dipoles and interfacial polarization enclosed by the polymers. The increased dielectric constant with PANI dosing as well as with temperature attributed to favorable interfacial polarization. Shifting of peak is noticed in the spectra of imaginary electric modulus with increase in temperature which indicates increased chain dynamics of polymers in the mat. Three‐dimensional analysis of the field emission scanning electron microscopy images was carried out by SPIP analytical software. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46121.     

Polyaniline Salts and Complexes as Catalyst in Bisindole Synthesis

Polyaniline salts are prepared by doping of polyaniline base with different Bronsted acids (H₂SO₄, HNO₃ and H₃PO₄), organic acid — p-toluene sulfonic acid (PTSA) and Iodine (I₂). Polyaniline complexes are also prepared using Lewis acids (BF₃, AlCl₃ and SnCl₂). Polyaniline salts and polyaniline complexes are characterized by physical, electrical and spectral methods. Polyaniline salts and polyaniline complexes are used as catalyst for the first time in bisindole synthesis. Bisindole (3,3′-bis(indolyl)phenylmethane) is obtained in excellent yields with simple and more environmental benign procedure. The use of polyaniline catalysts are feasible because of their easy preparation, easy handling, stability, easy recovery, reusability, good activity and eco-friendly.     

One-pot synthesis of soluble wholly aromatic liquid crystalline copoly(ester amide)s with high thermal and dimensional stability

Abstract

Thermotropic liquid crystalline polymers (LCPs) have been of great interest for electronic packaging. Herein, we introduce a series of wholly aromatic, thermotropic LCPs from copoly(ester amide)s of 6-hydroxy-2-naphthalic acid, isophthalic acid, terephthalic acid, and 4-aminophenol, prepared by a convenient one-pot melt polycondensation. Almost synthesized copoly(ester amide)s exhibited good solubility in common organic solvents at room temperature. Furthermore, they possessed high thermal stability with 2% degradation temperatures (T_id) of 359–368?°C and the char yields (at 600?°C) of 50.3–55.6%. The synthesized copoly(ester amide)s had relatively low coefficient of thermal expansion (CTE) values, which were 35.85–41.21?ppm °C^?1 in the temperature range of 50–200?°C. Furthermore, an annealing process could be employed to improve the thermomechanical properties of synthesized polymers. For instance, the CTE of sample LCP3 in range temperature of 275–315?°C was reduced by more than 90% after annealing at 320?°C for 1?h, implying the feasibility for electronic packaging.