Synthesis and characterization of a ferrocene‐modified,polyaniline‐like conducting polymer

A novel monomer called 1,1′‐ferrocenediacyl anilide (FcA) was synthesized from ferrocene (Fc). Copolymerization was carried out between FcA and aniline (ANI) by an electrochemical method. The novel monomer and copolymer were characterized with ¹H‐NMR, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet–visible (UV–vis) spectroscopy. The hydrogen protons of the benzene ring were moved to a low field in ¹H‐NMR, and the absorption band of N?Q?N (where Q is the quinoid ring) appeared in the FTIR spectrum of the polymer. The peaks of both Fc and the π–π* electronic transition in the UV–vis spectra were redshifted. The results indicate that the copolymer mainly existed as a highly delocalized conjugated system. X‐ray diffraction analysis established further proof, and the process of electrochemical deposition was observed by scanning electron microscopy. The optimal synthesis conditions of the copolymer were determined through changes in the monomer molar ratios and the scan rate. The ideal performance of the copolymer was gained when the monomer molar ratio between FcA and ANI was 1:4 and the scan rate was 50 mV/s. Furthermore, the electrochemical performances were tested in detail by cyclic voltammetry, galvanostatic charge–discharge testing, and electrochemical impedance spectroscopy. The results show that the specific capacitance of poly(1,1′‐ferrocenediacyl anilide‐co‐aniline) increased up to 433.1 F/g at 0.5 A/g, the diffusion resistance was very small, and the durability was good enough. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43217.     

Impedance spectroscopy of siloxane‐containing polyazomethines blended with SiO2

Two siloxane‐containing polyazomethines (PAZx) blended with SiO₂ were investigated. SiO₂ was obtained by sol‐gel method. The size of obtained SiO₂ particles was about 408 nm as was confirmed by SEM technique. For the blended with silica polymers absorption UV‐vis properties were tested and compare with unblended ones. Electrical behavior of the two kind devices indium tin oxide (ITO)/PAZx : SiO₂/Al and ITO/PEDOT : PSS/PAZx : SiO₂/Al were tested by impedance spectroscopy in dark and under illumination (halogen lamp, 100 mW/cm²) in the frequency range of 1 Hz to 1 MHz with maximum voltage value of 20 mV. For all measured devices, Nyquist plots were presented. PEDOT : PSS interlayer improved electrical properties of made prototype polymeric solar cells. Blending PAZx with silica increased conductivity from 10^–15 to 10^–8 S/cm. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Ion‐conducting polymer gels of polyacrylamide embedded with K2CO3

A highly ionic conductive solid‐gel membrane based on polyacrylamide hydrogels with a K₂CO₃ additive was investigated. The polymer‐based gel was prepared by adding ionic species K₂CO₃ to a monomer solution followed by polymerization. After polymerization, the ionic species was embedded in the polymer‐based gel, where it remained. The ionic species behaved like a liquid electrolyte, whereas the polymer‐based solid‐gel membrane provided a smooth impenetrable surface that allowed for the exchange of ions. The gel membranes were obtained in the form of thin films of reasonable mechanical strength. Their ambient temperature conductivities were in the range 10^?2 to 10^?1 S/cm. The effect of K₂CO₃ concentration on the conductivity of the gels prepared was examined in the temperature range from 0 to 100°C. The microstructure and chemical composition of the gels studied were characterized by environmental scanning electron microscopy and FTIR, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2076–2081, 2004     

New polymer syntheses part: 54 novel conducting polymers and copolymers based on 4‐Teriary butyl‐cyclohexanone moiety in the main chain

A new interesting class of conducting polymer and copolymers based on 4‐teriary butyl‐cyclohexanone in the main chain has been synthesized by solution polycodensation of terephthalaldehyde with 4‐teriary butyl‐cyclohexanone and/or cycloalkanone derivatives. The model compound I was synthesized from the 4‐teriary butyl‐cyclohexanone with benzaldehyde, and its structure was confirmed by elemental and spectral analyses. The resulting polymer and copolymers were characterized by elemental and spectral analyses including Fourier transform infrared spectrometer (FT‐IR) and nuclear magnetic resonance (¹H‐NMR), beside solubility and viscometry measurements. The thermal properties of those polymer and copolymers were evaluated by thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) measurements and correlated to their structural units. X‐ray analysis showed that it has some degree of crystallinity in the region 2θ = 5–60°. The UV–visible spectra of some selected polymers were measured in dimethyl sulfoxide (DMSO) solution and showed absorption bands in the range 253–398 nm, due to n–π* and π–π* transition. The morphological properties of selected examples were tested by scanning electron microscope (SEM). Moreover, the electrical conductivities and the doping with iodine were tested. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Biodegradation of in situ‐forming gel of poly(DLLA‐co‐CL) in vivo

Poly(dl ‐lactide‐co‐caprolactone) was dissolved in N‐methyl‐2‐pyrolidone (NMP) for preparing blank group formulation, and drug group was prepared by dissolving testosterone undecanoate (TU) as model drug in blank group. These formulations rapidly gelled by solvent diffusion effect after subcutaneous injection. The in vivo degradation of copolymer gel in rabbits was investigated after injection. The GPC and ¹H NMR results showed that no matter the gel contained drug or not, it had no effect on degradation rate for the P(DLLA‐co‐CL) carrier. Degradation products of copolymer were absorbed or excreted based on metabolism. Copolymer molar composition changed slightly in 3 months. The structures and characteristic of copolymers were characterized via DSC, TGA, and SEM, respectively. Experimental results showed that the copolymer had excellent heat resistance. Crystallinity increased gradually during degradation process. A dense cross‐sectional structure formed after 90 days. In addition, it can be obviously found that the degradation process of the copolymer proceeded in two steps. Mechanism of copolymer biodegradation in vivo was bulk degradation. The gel could well administrate the release of TU in a sustained way without significant burst features. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3800–3808, 2013     

Synthesis and chemical properties of electrochromic π‐conjugated polyphenylenes with pendant viologen‐TCNQ salts

Polyphenylene (PP) with NH₂ side groups, namely, PFluNH ₂ , was synthesized by the Pd‐catalyzed reaction of 2,5‐dibromoaniline with 9,9‐dihexylfluorene‐2,7‐diboronic acid bis(1,3‐propanediol) ester. The reaction of PFluNH ₂ with 1‐hexyl‐1′‐(2,4‐dinitrophenyl)‐4,4′‐bipyridinium diiodide ( SaltBPy(I^?) ) eliminated 2,4‐dinitroaniline to yield PPs with viologen (1,1′‐disubstituted 4,4′‐bipyridinium dications), PFluBPy(I^?) . The reaction of PFluBPy(I^?) with Li⁺TCNQ ^? resulted in anion exchange between Cl ^? and TCNQ ^? , and yielded PFluBPy(TCNQ^?) . The reaction of PFluBPy(TCNQ^?) with the neutral TCNQ⁰ resulted in an interaction between TCNQ ^? and TCNQ⁰, and yielded PFluBPy(TCNQ^?‐TCNQ⁰) . Cyclic voltammetry measurements suggested that an electrochemical reduction of the viologen moiety and oxidation of the polymer backbone within PFluBPy(TCNQ^?) and PFluBPy(TCNQ^?‐TCNQ⁰) . Furthermore, this reaction was accompanied by electrochromism. The electric conductivities (σ) of the pellets molded from PFluBPy(TCNQ^?) to PFluBPy(TCNQ^?‐TCNQ⁰) were 2.7 × 10 ^{? 4} and 4.2 × 10 ^{? 4} Scm ^{? 1}, respectively; these σ values were higher than that observed for PFluNH ₂ (σ < 10 ^{? 8} Scm ^{? 1}) due to the self‐doping in the polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Secondary dopants modified PEDOT‐sulfonated poly(imide)s for high‐temperature range application

Poly(3,4‐ethylenedioxythiophene) (PEDOT) was polymerized using sulfonated poly(amic acid)s templates (SPAA1 and SPAA2) by batch operation. The new method was invented to enhance conductivities (ca. 100 ‐ to 2000‐fold) and with less reaction time from previous work (7 days vs. 3 days). Moreover, to increase the conductivity, many dopants were introduced as secondary doping compared with DMF, D ‐sorbitol, and surfynol that were previously used. After annealing at 180°C for 10 min, PEDOT‐SPAA1 and PEDOT‐SPAA2 doped with benzo‐1,4‐dioxan and quinoxaline showed the increase in conductivity by higher percentage than any other systems, especially doped with D ‐sorbitol and surfynol. These showed the promising tendency to develop the annealing activated superior conductivity materials after further modifying the conducting film forming processes. However, PEDOT‐SPAAs doped with benzo‐1,4‐dioxan, imidazole and quinoxaline via annealed at 180°C for 10 min were found to be more conductive than doped with DMF, but still lower conductive than doped with D ‐sorbitol and surfynol. In terms of particle size, the stable aqueous dispersions of conducting polymers prepared were comparable to polystyrene sulfonate template. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a PPV‐fluorene derivative: Applications in luminescent devices

Synthesis of a polyfluorene/poly(p‐phenylene vinylene) derivative, the Poly [(9,9′‐di‐hexylfluorenediylvinylene‐alt‐1,4‐phenylenevinylene)‐co‐((9,9′‐(3‐t‐butylpropanoate) fluorene‐1,4‐phenylene)] (LaPPS 42) was performed following Wittig and Suzuki routes. Polyfluorenes and derivatives have been used in electroluminescent devices, and the synthesis described here has the advantage in pave the way to get distinct structures having different emission spectra. An extensive study of its electrochemical, thermomechanical, optical, and structural properties was carried out, as well as its application in electroluminescent devices. Polymer light‐emitting diodes (PLEDs) and polymer light‐emitting electrochemical cells (PLECs) were built using LaPPS 42 as active layer, and their electric and optical characterizations confirm they have a potential as active element in electroluminescent devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42579.     

Synthesis of two D‐π‐A polymers π‐bridged by different blocks and investigation of their photovoltaic property

The synthesis, characterization, photophysical and photovoltaic properties of two 5,6‐bis(octyloxy)benzo[c][1,2,5]thiadiazole‐containing wide‐band‐gap donor and acceptor D‐π‐A alternating conjugated polymers (HSD‐a and HSD‐b) have been reported. These two polymers absorb in the range of 300–700 nm with a band gap of about 1.88 and 1.97 eV. The HOMO energy levels were ?5.44 eV for HSD‐a and ?5.63 eV for HSD‐b. Polymer solar cells with HSD‐b :PC₇₁BM as the active layer demonstrated a power conversion efficiency (PCE) of 2.59% with a high V_oc of 0.93 V, a J_sc of 7.3 mA/cm², and a comparable fill factor (FF) of 0.38 under simulated solar illumination of AM 1.5G (100 mW/cm²) without annealing. In addition, HSD‐a :PC₇₁BM blend‐based solar cells exhibit a PCE of 2.15% with a comparable V_oc of 0.64 V, J_sc of 8.75 mA/cm^?2, and FF of 0.40. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41587.     

Electrical properties of sorbitol‐doped poly(vinyl alcohol)–poly(acrylamide‐co‐acrylic acid) polymer membranes

Solid polymer membranes from poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐acrylic acid) (PAA) with varying doping ratios of sorbitol were prepared using the solution casting method. The films were examined with Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and AC impedance spectroscopy. The impedance measurements showed that the ionic conductivity of PVA–PAA polymer membrane can be controlled by controlled doping of sorbitol within the polymer blends. The PVA–PAA–sorbitol membranes were found to exhibit excellent thermal properties and were stable for a wide temperature range (398–563K), which creates a possibility of using them as suitable polymers for device applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Specroelectrochemical,switching kinetics,and chronoamperometric studies of dibenzyl derivative of poly(3,4‐propylenedioxythiophene) thin‐film‐based electrochromic device

The dibenzyl derivative of poly(3,4‐propylenedioxythiophene) (PProDOT‐Bz₂) thin film is deposited onto ITO‐coated glass substrate by electropolymerization technique. The electropolymerization of ProDOT‐Bz₂ is carried out by a three‐electrode electrochemical cell. The cyclic voltammogram shows the redox properties of electrochemically prepared films deposited at different scan rates. The thin films prepared were characterized for its morphological properties to study the homogeniety. Classic six‐layer structure of PProDOT‐Bz₂ electrochromic device using this material was fabricated and reported for the first and its characterizations such as spectroelectrochemical, switching kinetics, and chronoamperometric studies are performed. The color contrast of the thin film and the device achieved are 64 and 40%, respectively, at λ_max (628 nm). The switching time is recorded and the observed values are 5 s from the coloring state to the bleaching state and vice versa. The chronoamperometry shows that the device performed up to 400 cycles, and it is capable of working up to 35 cycles without any degradation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40717.     

The electropolymerization of several poly(3‐methylthiophene) films in the same used solution and its consequence in their properties

The effect of the electropolymerization of seven poly(3‐methylthiophene) (P3MT) films in the same used monomer solution have been investigated. Cyclic voltammetry, UV‐visible, scanning electron microscopy, and electrochemical impedance measurements were carried out to understand the effect of the solution reusing on the polymer electrochemical properties. The obtained results show that, as the solution is reused, the polymerization rate increase and the charge in of the cyclic voltammetry decrease. Besides, there are important changes in the sample's morphologies, with the increase of the synthesis number, the amount of fibers increase and this leads to lower the conductivity of the polymer film. In agreement to this, the impedance data analysis shown important changes in the interfacial electronic parameters, i.e., changer transfer resistance and double‐layer capacitance, used to describe the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44368.     

Synthesis and characterization of conducting homopolymers and copolymers of o‐anisidine and o‐toluidine in inorganic and organic supporting electrolytes

The influence of inorganic and organic supporting electrolytes on the electrochemical, optical, and conducting properties of poly(o‐anisidine), poly(o‐toluidine), and poly(o‐anisidine‐co‐o‐toluidine) thin films was investigated. Homopolymer and copolymer thin films were synthesized electrochemically, under cyclic voltammetry conditions, in aqueous solutions of inorganic acids (H₂SO₄, HCl, HNO₃, H₃PO₄, and HClO₄) and organic acids (benzoic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, and adipic acid) at room temperature. The films were characterized by cyclic voltammetry, ultraviolet–visible spectroscopy, and conductivity measurements with a four‐probe technique. The ultraviolet–visible spectra were obtained ex situ in dimethyl sulfoxide. The optical absorption spectra indicated that the formation of the conducting emeraldine salt (ES) phase took place in all the inorganic electrolytes used, whereas in organic acid supporting electrolytes, ES formed only with oxalic acid. Moreover, the current density and conductivity of the thin films was greatly affected by the nature and size of the anion present in the electrolyte. For the copolymer, the conductivity lay between the conductivity of the homopolymers, regardless of the supporting electrolyte used. The formation of the copolymer was also confirmed with differential scanning colorimetry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2634–2642, 2003     

Chitosan‐based gel film electrolytes containing ionic liquid and lithium salt for energy storage applications

Fabrication, characterization, and a comparative study have been performed for chitosan‐based polymer electrolytes using two different dispersion media. Chitosan gel film (solid) electrolytes are fabricated using acetic acid or adipic acid as the dispersant for chitosan in combination with ionic liquid and lithium salt. This quaternary system of chitosan, acetic acid or adipic acid, 1‐butyl‐3‐methylimadazolium tetrafluoroborate (ionic liquid), and lithium chloride is formed as an electrolyte for potential secondary energy storage applications. The ionic conductivities, thermal, structural, and morphological properties for these electrolytes are compared. The ionic conductivities for chitosan/adipic acid (CHAD) and for chitosan/acetic acid (CHAC) systems are in the range of 3.71 × 10⁻⁴−4.6 × 10⁻³ and 1.3 × 10⁻⁴ −3.2 × 10⁻³ S cm⁻¹, respectively. The thermal stability of CHAD‐based electrolytes is determined to be higher than that of CHAC‐based electrolytes. Preliminary studies are performed to determine the electrochemical stability of these materials as solid film electrolytes for electrochemical supercapacitors. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42143.     

Effect of propylene carbonate on the ionic conductivity of polyacrylonitrile‐based solid polymer electrolytes

Solid polymer electrolyte membranes consisting of polyacrylonitrile (PAN) as a host polymer, ammonium nitrate (NH₄NO₃) as a complexing salt, and propylene carbonate (PC) as a plasticizer were prepared by a solution casting technique. An increase in the amorphous nature of the polymer electrolytes was confirmed by X‐ray diffraction analysis. A shift in the glass‐transition temperature of the PAN/NH₄NO₃/PC electrolytes was observed in the differential scanning calorimetry thermograms; this indicated interactions between the polymer and the salt. The impedance spectroscopy technique was used to study the mode of ion conduction in the plasticized polymer electrolyte. The highest ionic conductivity was found to be 7.48 × 10^?3 S/cm at 303 K for 80 mol % PAN, 20 mol % NH₄NO₃, and 0.02 mol % PC. The activation energy of the plasticized polymer electrolyte (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) was found to be 0.08 eV; this was considerably lower than that of the film without the plasticizers. The dielectric behavior of the electrolyte is discussed in this article. A literature survey indicated that the synthesis and characterization of ammonium‐salt‐doped, proton‐conducting polymer electrolytes based on PAN has been rare. The use of the best composition membrane (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) proton battery was constructed and evaluated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41743.     

Anhydrous proton‐conducting electrolyte based on a nematic poly(methyl acrylate) containing sulfonated side chains

A nematic poly(methyl acrylate) containing terminal sulfonic acids in side chains was prepared by etherification of a brominated mesomorphic precursor with 2‐hydroxyethanesulfonic acid sodium salt. Differential scanning calorimetry measurements and polarized light microscopy observation revealed that the sulfonated polymer exhibited the nematic mesophase at medium temperatures (189–227°C). Electrochemical impedance spectroscopy measurements showed that temperature dependence of anhydrous proton conductivity for the nematic polymer followed the Arrhenius law and that the estimated activation energy was 95 kJ mol⁻¹ in the nematic phase. The proton conductivities of the nematic polymer were two orders of magnitude higher than those of anhydrous Nafion®117 membrane at the same temperature. The enhanced anhydrous proton conductivities of the polymeric electrolyte were ascribed to the orientational order and fluidity of the nematic liquid crystal. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40382.     

Investigation of the extraction process in gel‐spinning technology for ultrahigh‐molecular‐weight polyethylene fibers by low‐field nuclear magnetic resonance

A portable, low‐field nuclear magnetic resonance scanner, the nuclear magnetic resonance mobile universal surface explorer, is introduced as a tool for investigating the extraction process of mineral oil in the gel‐spinning technology of ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers. Factors affecting the extraction process were studied systematically; these included the UHMWPE type, extraction agent type, and concentration and ultrasound. We found that the extraction process could be described by a replacement–dilution dual‐effect model. The extraction agent not only replaced and extracted the mineral oil but also considerably decreased the viscosity of mineral oil and thus enhanced the molecular motion and diffusion of mineral oil. Although chloroform had a smaller molecular size and lower boiling point, benzene and cyclohexane were found to exhibit more efficient extraction and dilution effects on mineral oil. The extraction efficiency could be characterized by the diffusion of mineral oil in the mineral oil/UHMWPE gel/deuterated extraction agent multicomponent systems during the extraction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42018.     

Nanostructured star‐shaped polythiophene with tannic acid core: Synthesis,characterization, and its physicochemical properties

For the first time, synthesis and characterization of a nanostructured star‐shaped polythiophene (PTh) with tannic acid core by both chemical and electrochemical oxidation polymerization methods through a “core‐first” method is reported. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared (FTIR), and ¹H nuclear magnetic resonance (NMR) spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions, and their conductivities were determined using the four‐probe technique. The synthesized star‐shaped PTh showed higher electrical conductivity and electroactivity than those of the PTh in both chemical and electrochemical polymerized samples, due to its large surface area, spherical, and three‐dimensional structure. Moreover, the thermal behaviors, optical properties, and morphologies of the synthesized samples were investigated by means of thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, and field emission scanning electron microscopy (FE‐SEM), respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43513.     

Investigations of the electrical conduction mechanisms of polyaniline‐DBSA/poly(acrylonitrile‐butadiene styrene) blends

The electrical properties of Al/PANI‐DBSA/ABS/Au blend with PANI (5%) w/w have been investigated by using of current‐voltage (I‐V) measurements, in a temperature range of 100–313 K. The analysis of I‐V characteristics in the forward direction was based on thermionic emission mechanism for applied electrical field till ～3 × 10² V/cm. The thickness dependence of the current‐voltage relationship, clearly demonstrates that the electrical current for larger fields is space charge limited current (SCLC). Temperature dependences of the ideality factor, barrier height, and series resistance have been calculated. The mobility of carriers which is temperature dependent was calculated using the trap free SCLC as 1.53 × 10^?4 cm² V^?1 s^?1 at room temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40688.