Structural,electrical, thermal,and gas sensing properties of new conductive blend nanocomposites based on polypyrrole/phenothiazine/silver‐doped zinc oxide

The main aim of this study is to investigate the effect of silver‐doped zinc oxide (Ag‐ZnO) loading on the structural, morphological, thermal and electrical properties, and gas sensing behavior of polypyrrole (PPy)/phenothiazine (PTZ)‐blend nanocomposites. The composites are characterized by FTIR, XRD, SEM, TEM, DSC, TGA, and impedance studies. FTIR spectra exhibit the presence of Ag‐ZnO in the PPy/PTZ blend. XRD analysis shows that the semicrystalline behavior of the polymer blend is greatly enhanced by the addition of Ag‐doped ZnO particles. Uniform dispersion of nanoparticles in the polymer is obtained from SEM analysis. The TEM images confirm the presence of spherically shaped nanoparticles in PPy/PTZ blend with a size of 10–25 nm. The DSC measurement indicates that the glass transition temperature of PPy/PTZ blend was significantly improved in the presence of Ag‐doped ZnO nanoparticles. The thermal decomposition temperature of nanocomposite obtained from TGA shows an increase with increase in the content of Ag‐ZnO particles. The incorporation of Ag‐doped ZnO nanoparticles to PPy/PTZ blend exhibit increase in the AC conductivity and dielectric properties of the nanocomposite, due to the pilling of charges at the extended interface of the composite system. The DC conductivity of the nanocomposite increases with the loading of nanoparticles. The ammonia gas sensing performance of PPy/PTZ/Ag‐ZnO nanocomposite is analyzed, and the result shows that the fabricated blend composite can be used as a promising candidate for the easy access of gas molecules. J. VINYL ADDIT. TECHNOL., 26:187–195, 2020. © 2019 The Authors. Journal of Vinyl and Additive Technology published by Wiley Periodicals, Inc. on behalf of Society of Plastics Engineers.     

In Situ Synthesis,Characterization and Conductivity of Copper Sulphide/Polypyrrole/Polyvinyl Alcohol Blend Nanocomposite

This work focused on the preparation, characterization and conductivity studies of copper sulphide nanoparticle incorporated polypyrrole (PPy)/polyvinyl alcohol (PVA) blend by in situ chemical oxidative polymerization. The blend nanocomposites were examined by FTIR, SEM, XRD, TGA and electrical studies. The complexation of CuS with the polymer was confirmed by FTIR. The surface observed in the SEM image clarifies the uniformity in morphology. The XRD pattern reveals that the nanoparticle incorporated PPy and their blend showed a crystalline nature. TGA and conductivity studies indicated that the blend nanocomposites attain better thermal stability and conductivity than original polypyrrole and PPy/PVA blend.     

Insights on tunneled electrons for electrical and photoelectric behaviors in conducting multilayer films

We demonstrate here the layer‐by‐layer (LbL) self‐assembly of conducting [poly(styrene sulfonate)‐poly(vinyl alcohol)/polypyrrole]_n [(PSS‐PVA/PPy)_n] multilayer film with interesting electrical and photoelectric features. Increments in sheet conductivity and photoelectric response with increasing bilayer number are pioneerly recorded. The fantastic phenomenon is determined as the accumulative electrons tunneled across insulating PSS from bottom to top PPy chains. The resulting multilayer films give a linear growth in bulk conductivity and maximum photocurrent density. Careful examination of data and characterizations indicates that the fantastic effects in electrical conduction and photocurrent are accumulative electrons tunneled across PSS from bottom to top PPy. POLYM. ENG. SCI., 55:107–112, 2015. © 2014 Society of Plastics Engineers     

Synthesis and characterization of montmorillonite/polypyrrole nanocomposite

A novel montmorillonite (MMT)/polypyrrole (PPy) nanocomposite (MPN) with high electrical conductivity and thermal stability has been synthesized via in‐situ polymerization. The surface morphology, characterization, thermal stability, and electrical conductivity have been tested by scanning electron microscopy (SEM), Fourier‐transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and four‐probe methods, respectively. SEM results show that the antenna‐like PPy deposits on the layer surface of MMT. FTIR and XRD analyses show that there is interaction between MMT and PPy. The nanocomposite has high electrical conductivity (4 S/cm), eight orders of magnitude higher than that of pristine MMT. The thermal stability of MPN is higher than the pure PPy as well as the mixture of MMT and PPy (MMP). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Characterization and physical properties investigation of conducting polypyrrole/TiO2 nanocomposites prepared through a one‐step “in situ” polymerization method

Nowadays, nanocomposites are a special class of materials having unique physical properties and wide application potential in diverse areas. The present research work describes an efficient method for synthesis of a series of polypyrrole/titanium dioxide (PPy/TiO₂) nanocomposites with different TiO₂ ratios. These nanocomposites were prepared by one‐step in situ deposition oxidative polymerization of pyrrole hydrochloride using ferric chloride (FeCl₃) as an oxidant in the presence of ultra fine grade powder of anatase TiO₂ nanoparticles cooled in an ice bath. The obtained nanocomposites were characterized by Fourier‐transform infrared (FTIR), thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and scanning electron microscope (SEM) techniques. The obtained results showed that TiO₂ nanoparticles have been encapsulated by PPy with a strong effect on the morphology of PPy/TiO₂ nanocomposites. Also, the synthesized PPy/TiO₂ nanocomposites had higher thermal stability than that of pure PPy. The investigation of electrical conductivity of nanocomposites by four‐point probe instrument showed that the conductivity of nanocomposite at low TiO₂ content is much higher than of neat PPy, while with the increasing contents of TiO₂, the conductivity decreases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal Behaviors of Bisazocalix[4]arene Derivatives

In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting from 25,27-dibenzoyl-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene (2). Azocalix[4]arenes (6a-c) were coupled by linking 4-methoxy, 4-ethyl, and 4-nitroaniline to calix[4]arene (4) through a diazo-coupling reaction. Thermal behavior characteristics and decomposition routes of 25,26,27,28-tetrahydroxy-11,23-di(tert-butyl)-5,17-(p-substitue phenyl)azocalix[4]arene (6a-c) were investigated in air atmosphere by means of thermogravimetry (TG), differential thermogravimetry (DTG), and differential thermal analysis (DTA) analyses. It was found that the decomposition of all compounds complete with two exothermic stages which corresponded to removal of substitute groups (methoxy-, ethyl-, nitro-) and second stage rest of structure decomposition.     

Synthesis and investigation of properties of thiacalix[4]arene‐based polyurethane elastomers

A series of polyurethane elastomers (PUEs) derived from three thiacalix[4]arene derivatives (TC4As), namely p‐tert‐butylthiacalix[4]arene, tetrasodium thiacalix[4]arenetetrasulfonate and thiacalix[4]arenetetrasulfonic acid, as a portion of chain extender in a mixture with glycerol were synthesized. The effects of the chemical structure of TC4As used as chain extenders on the various properties of the prepared PUEs were investigated and compared with PUE extended with only glycerol as chain extender using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X‐ray diffraction (XRD), scanning electron microscopy and a universal tensile tester. Moreover, the effect of the introduction of TC4As as a portion of chain extender on the hydrophobicity of the PUEs was also evaluated. DSC, FTIR spectroscopy and XRD revealed that the degree of phase separation and crystallinity in TC4A‐based PUEs was much higher than that of the glycerol‐based ones. Thus, it was concluded that the presence of TC4As in TC4A‐based PUEs seems to favour the formation of a more ordered structure due to an increase in the degree of phase separation. The TGA results also showed that, with incorporation of TC4As into the polyurethane backbone, the thermal stability of PUEs was improved. © 2014 Society of Chemical Industry     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel Ni/polypyrrole and Cu/polypyrrole composites prepared in the presence of different acids: Synthesis and investigation of thermal stability

We report the synthesis and characterization of new organic/inorganic hybrid materials constituted of Ni(0) and Cu(0) nanoparticles and polypyrrole (PPy). Copper and nickel nanoclusters were synthesized by a chemical reduction of aqueous metal salt solutions by sodium borohydride. PPy/Ni(0) and PPy/Cu(0) composites were obtained in the presence of two different acids (H₃BO₃, CH₃COOH), by polymerizing pyrrole‐Ni and pyrrole‐Cu particles by using iron (III) chloride. The composites have been characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and magnetic susceptibility techniques. Conductivity measurements of samples were taken using four‐probe devices. The PPy/Ni(0) and PPy/Cu(0) nanocomposites doped with different acids exhibited higher conductivity values than those of homopolymers. Among all samples, Ni/PPy‐H₃BO₃ has the highest conductivity (1.42 S cm^?1). Homopolymers and composites showed a stable and increasing conductivity with increasing temperature, except Ni(0). We observed that from TGA analysis of polymers, metal composites of PPy synthesized in two different media are more stable than those of PPy‐CH₃COOH and PPy‐H₃BO₃. The magnetic susceptibility values of homopolymers and Cu are negative, whereas the other samples are positive. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

A New High-Temperature Lithium Para-Toluene Sulfonate (LIPTSA) Salt for Rechargeable Batteries

Lithium para-toluene sulfonate [LIPTSA] was used for lithium rechargeable batteries, with poly(methyl methacrylate) [PMMA] as the base material. Tri block copolymer of PEO-PPO-PEO was used to increase the solubility of lithium salts in PMMA matrix. FTIR, TGA, XRD, impedance spectroscopy, and SEM were used for characterizations and morphological studies. LIPTSA salt is stable up to 375°C. The highest room temperature conductivity obtained was around 5 × 10^?4 Scm^?1. The SEM picture shows clearly the heterogeneous morphology (salt-rich phases) distributed throughout the PMMA matrix. The XRD picture indicates the presence of crystalline, which increases with an increase in salt concentration.     

Synthesis and characterization of soluble polypyrrole with improved electrical conductivity

Polypyrroles doped with two dopants were prepared by chemical polymerization in aqueous solutions of pyrrole monomer. The solutions contained dodecylbenzenesulfonic acid (DBSA) as a dopant, tetraethylammonium tetrafluoroborate (TEABF₄) as a codopant, and ammonium persulfate (APS) as an oxidant. The PPy composites [polypyrrole‐dodecylbenzenesulfonates (PPy‐DBS) codoped with tetrafluoroborate (BF)—PPy‐DBS‐BF] were soluble in m‐cresol, NMP, and conditionally soluble in chloroform. Cyclic voltammetry was measured to know the electrochemical property of PPy‐DBS‐BF. The maximum electrical conductivity of room temperature for PPy‐DBS‐BF is 1.18 s/cm, which is greatly higher than that of polypyrrole doped with DBS^? (0.04 s/cm). The composition and structural characterization of PPy‐DBS‐BF were inferred from elemental analysis, nuclear magnetic resonance, and Fourier transform infrared spectroscopy. Scanning electron microscopy was performed to know the morphology of PPy‐DBS‐BF. The results of UV‐Vis spectra and electron spin resonance measurements showed that polaron and bipolaron existed as charge carrier of soluble PPy‐DBS‐BF. From the temperature dependence of the electrical conductivity, it was suggested that possible conduction mechanism for soluble PPy‐DBS‐BF should be hopping conduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2583–2590, 2002     

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole PolyHIPE composite foam prepared by chemical oxidative polymerization

Conducting poly(styrene‐co‐divinylbenzene)/polypyrrole (PPy) polyHIPE (polymerized high internal phase emulsion) composite foams were synthesized via chemical oxidative polymerization method. The effect of solvent and dopant type on the surface morphology and electrical conductivity of composite foams has been investigated. SEM micrographs showed that the morphology of PPy thin film on the internal surface of poly(styrene/divinylbenzene) (poly(St‐co‐DVB) polyHIPE support foam strongly depends on the solvent and dopant type used. Incorporation of dodecylbenzene solfunic acid‐sodium salt (DBSNa) as a dopant in chloroform solvent resulted in formation of a PPy thin film with higher molecular compact structure and electrical conductivity on the support foam as compared to other solvents and another dopant used. Fourier‐transform infrared spectroscopy was used to correlate the electrical conductivity of composite foams to their PPy structural parameters. As expected, the extended conjugation length of PPy in the presence of DBSNa dopant is the main reason for higher electrical conductivity of resultant composite foam. Electrical conductivity measurements revealed that the chemical aging of various conducting foams follows the first‐order kinetic model, which is a representative of a reaction‐controlled aging mechanism. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric studies of composite paper reinforced with polypyrrole coated pulp fibers from wasted egg holders

Development of thin, flexible, light‐weight, renewable, low‐cost, and environmentally friendly electrode materials are highly feasible in era of modern disposable electronic technology. This article presents the synthesis and dielectric studies of polypyrrole (PPy) coated pulp fibers, directly collected from wasted egg holder's tray. PPy coated pulp fibers converted into compact sheet for the development of potential renewable and low‐cost electrode materials. The morphology, chemical structure, and thermal stability of naked and PPy coated pulp fibril sheets were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and thermogravimetric analysis (TGA), respectively. PPy coated pulp fibers revealed better thermal stability and compactness of sheet morphology. Impedance measurements showed a high value of dielectric constant of 1.15 × 10⁶ at 0.5 Hz and conductivity of 7.45 × 10^?4 S/cm at room temperature for PPy coated pulp fibril sheet. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42422.     

Synthesis,Characterization, and Combustion Catalytic Activities of Copper(II) and Lead(II) Salts of p‐Nitrocalix[n]arenes (n=4, 6, 8)

Six copper(II) and lead(II) salts of p‐nitrocalix[n]arene (n=4, 6, 8) were synthsized and characterized. The DSC curves of all salts showed exothermic decomposition. Sensitivity studies revealed that all the salts with the exception of the lead salt of p‐nitrocalix[6]arene (NCPb6) are relatively insensitive materials. Investigations of the catalytic activities showed that most of the salts displayed high activities in thermal decomposition of NC‐NG and RDX. As evaluated in this work, the salts enhanced the burning rates of both double base (DB) and RDX‐component modified double base propellants. The best catalytic effect was obtained with NCPb6, which increased the burning rate of the DB propellant to the order of about 200 % (2–6 MPa) and 103–198 % (8–20 MPa) while decreasing the pressure index (n) to 0.22 (20–22 MPa).     

Physical and potentiometric properties of polyurethane‐based cation‐selective membranes

Lipophilic salts based on tetraphenylborate derivatives [e.g., potassium tetrakis(p‐chlorophenyl)borate (KTpClPB), sodium tetraphenylborate (NaTPB), and cesium tetrakis(3‐methylphenyl)borate are essential ingredients used in the preparation of solvent polymeric cation‐selective membranes. The effects of such lipophilic salts on the physical properties of a polyurethane (PU) matrix comprising 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol, and poly(tetramethylene ether glycol) were examined. Differential scanning calorimetry measurements revealed that the sodium and potassium salts doped in PU increased the glass‐transition temperatures (T_g) of the matrix, while the film containing cesium salt exhibited slightly decreased T_g. The temperature dependence of the ionic conductivity for PU60 films doped with KTpClPB is well described by the Arrhenius‐type equation, and that doped with NaTPB is described by the Vogel–Tammann–Fulcher (VTF)‐type equation. The temperature dependence of the ionic conductivity on the VTF‐type equation suggests that the transport of sodium ions in the PU60 matrix is more strongly coupled to the soft segmental motion, and potassium ions are decoupled from the polymer host and transported by activated hopping. The effect of added salt on the internal structure of PU membranes was investigated by measuring the ratio between the free and hydrogen‐bonded CO bands at 1703 and 1730 cm⁻¹, respectively. The results showed that the ether oxygens in the soft segment chains are strongly coupled to the potassium or sodium, but much less to cesium. The potentiometric properties of these lipophilic additive doped PU membranes were characterized by incorporating valinomycin and 4‐tert‐butylcalix[4]arene‐tetraacetic acid tetraethylester as potassium‐ and sodium‐selective ionophores, respectively. Their response behavior could be explained by the observed physical characteristics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 618–625, 2001     

Chromatographic partitioning of cesium by a macroporous silica‐calix[4]arene‐crown supramolecular recognition composite

A macroporous silica‐based 1,3‐[(2,4‐diethyl‐heptylethoxy)oxy]‐2,4‐crown‐6‐calix[4]arene (Calix[4]arene‐R14) supramolecular recognition polymeric composite, (Calix[4]+Oct)/SiO₂‐P, was synthesized. It was performed by impregnating and immobilizing Calix[4]arene‐R14 and n‐octanol into the pores of the macroporous SiO₂‐P particles support. n‐Octanol was used to modify Calix[4]arene‐R14 through hydrogen bonding. The effect of eight typical fission products contained in highly active liquid waste (HLW) on the adsorption of Cs(I), one of the heat generators, was investigated at 298 K by examining the effect of contact time and the HNO₃ concentration in a range of 0.3–7.0 M. (Calix[4]+Oct)/SiO₂‐P showed excellent adsorption ability and high selectivity for Cs(I) at 4.0 M HNO₃ over the tested elements. The partitioning of Cs(I) from a simulated HLW was operated by (Calix[4]+Oct)/SiO₂‐P packed column. Cs(I) was able to be effectively eluted by water and separated from the tested metals. It is demonstrated that (Calix[4]+Oct)/SiO₂‐P is promising to apply in chromatographic separation of Cs(I) from HLW. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Pyrrole/N‐p‐toluenepyrrole copolymers in the presence of surfactants: A promising material for glucose sensing

In this study, pyrrole/N‐para‐toluenpyrrole (Py/NptPy) copolymers were synthesized by chemical oxidative polymerization method. The effects of different kinds of (anionic, cationic, and nonionic) surfactants on the properties of copolymer were investigated. The structural, morphological, thermal, and conductivity properties of the copolymers were investigated by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and the four‐probe measurement device respectively. FTIR spectra of copolymers synthesized in different environments that support the formation of copolymer. SEM results show that the morphologies of copolymers synthesized in the presence of surfactant are more homogeneous and the particle sizes are smaller than that of polypyrrole (PPy). TGA results revealed that the thermal stabilities of Py/NptPy‐NaDBS (400°C) and Py/NptPy‐Tween 20 (260°C) copolymers were higher than surfactant free Py/NptPy copolymer (180°C) according to their initial decomposition temperatures. It was determined that the conductivity values of copolymers were higher than PNptPy. Glucose sensor properties of copolymer synthesized in the presence of tetradecylthreemethyl ammonium bromide (TTAB) were investigated with cyclic voltammetry (CV) method. Michaelis–Menten constant of Py/NptPy‐TTAB copolymer modified electrochemical biosensor was calculated as 5.30 mM. POLYM. ENG. SCI. 56:995–1003, 2016. © 2016 Society of Plastics Engineers     

Preparation and characterization of conductive and magnetic PPy/Fe3O4/Ag nanocomposites

In this article, conductive and magnetic nanocomposites composed of polypyrrole (PPy), magnetite (Fe₃O₄) nanoparticles (NPs), silver (Ag) NPs, have been successfully synthesized with a two step process. First, the PPy/Fe₃O₄ was prepared by the ultrasonic in situ polymerization. Next, the PPy/Fe₃O₄/Ag was synthesized through the electrostatic adsorption. The products were characterized by fourier‐transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), Thermogravimetric (TG), conductivity and magnetization analysis, and the results showed that the Ag NPs with the good conductivity coated uniformly on the surface of PPy/Fe₃O₄ and improved the conductivity of PPy/Fe₃O₄/Ag composites. In addition, as compared with PPy/Fe₃O₄, PPy/Fe₃O₄/Ag composites also have the excellent electro‐magnetic property and enhanced thermostability. POLYM. COMPOS., 35:450–455, 2014. © 2013 Society of Plastics Engineers     

Soluble conducting polypyrrole doped with DBSA–CSA mixed acid

Soluble conductive polypyrrole (PPy) with room temperature conductivity (2–18 S/cm) has been synthesized by doping polypyrrole with mixed acid containing camphor sulfonic acid (CSA) and dodecyl benzene sulfonic acid (DBSA). The solubility and the room temperature conductivity of PPy doped with mixed acid were measured as a function of component of CSA–DBSA mixed acid, and the structure of PPy was characterized by Fourier transform infrared (FTIR), ultraviolet–visible (UV-vis) spectra, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). PPy doped with DBSA–CSA mixed acid is soluble in m-cresol although PPy doped only by CSA is completely insoluble in any solvent. The solubility of PPy doped with mixed acid increases with an increase in the fraction of DBSA in the mixed acid, while the room temperature conductivity of the PPy increases with increasing CSA molar fraction. The UV-vis spectra and electron spin resonance (ESR) measurements showed that both polaron and bipolaron are the charge carrier in the doped PPy with mixed acid. It was proposed that the contribution of CSA to the solubility of PPy doped with mixed acid is to decrease the interaction among PPy chains due to the large molecular size of CSA, while DBSA contributes to the solubility by its good solvating effect derived from its long alkyl chain. These may be a reason that both the solubility and conductivity of PPy are improved by the presence of CSA compared with those of PPy doped only with DBSA. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1277–1284, 1998