An observation on vibrational behaviour of undoped and doped poly(aniline) prepared by electrochemical polymerisation of aniline

Polyaniline has been prepared by electrochemical oxidation of aniline in an acidic medium. The pure polymer has been doped with iodine. The conductivity of the doped sample shows an increase of four order of magnitude than that of the undoped one. The characteristic observations made in the i.r. and Raman spectra have been discussed.     

Mechanochemical synthesis of poly(2,5-dimethoxy aniline) nanobelts and its electrochemical performance in hybrid supercapacitors

A solvent-free mechanochemical route for the preparation of poly(2,5-dimethoxyaniline) hydrochloride nanostructures is developed and reported in the article. High conductivity, good crystallinity, and nanostructured morphology are observed for the prepared polymer. This polymeric powder is utilized as a cathode material in hybrid supercapacitor and its electrochemical performance is evaluated and discussed in this short report. The maximum specific capacitance of the poly(2,5-dimethoxyaniline) hydrochloride/activated carbon hybrid supercapacitor is found to be 125 F g⁻¹ at 1 mA cm⁻² current density. The cell delivers a specific energy as high as 50 Wh kg⁻¹ at a specific power of 97 W kg⁻¹ and also exhibits an excellent cycle performance with more than 99% coulombic efficiency and the maintenance of 85% of its initial capacitance after 1,000 cycles.     

Electrochemical polymerization of alizarin and the electrochemical properties of poly(alizarin)

Electrochemical polymerization of alizarin on glassy carbon electrode (GCE) was carried out in acidic solution by cyclic voltammetry (CV), and the polymerization process was monitored by electrochemical quartz crystal microbalance (EQCM). A possible mechanism concerning the polymerization of alizarin was also proposed in this work. The as-synthesized poly(alizarin) was characterized by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The study on electrode reaction process shows that the electrode reaction of poly(alizarin) is controlled by diffusion. Finally, the activation energy (E _a) of the electrode reactions of poly(alizarin) was obtained according to the temperature dependence of the redox peak currents.     

Thermal and electrochemical properties of poly(butylene sulfite)-based polymer electrolyte

Poly(butylene sulfite) (poly-1) was synthesized by cationic ring-opening polymerization of butylene sulfite (1), which was prepared by the reaction of 1,4-butanediol and thionyl chloride, with trifluoromethanesulfonic acid (TfOH) in bulk. The polymer electrolytes composed of poly-1 with lithium salts such as bis(trifluoromethanesulfonyl)imide (LiN(SO₂CF₃)₂, LiTFSI) and bis(fluorosulfonyl)imide (LiN(SO₂F)₂, LiFSI) were prepared, and their ionic conductivities, thermal, and electrochemical properties were investigated. Ionic conductivities of the polymer electrolytes for the poly-1/LiTFSI system increased with lithium salt concentrations, reached maximum values at the [LiTFSI]/[repeating unit] ratio of 1/10, and then decreased in further more salt concentrations. The highest ionic conductivity values at the [LiTFSI]/[repeating unit] ratio of 1/10 were 2.36?×?10^?4 S/cm at 80 °C and 1.01?×?10^?5 S/cm at 20 °C. On the other hand, ionic conductivities of the polymer electrolytes for the poly-1/LiFSI system increased with an increase in lithium salt concentrations, and ionic conductivity values at the [LiFSI]/[repeating unit] ratio of 1/1 were 1.25?×?10^?3 S/cm at 80 °C and 5.93?×?10^?5 S/cm at 20 °C. Glass transition temperature (T _g) increased with lithium salt concentrations for the poly-1/LiTFSI system, but T _g for the poly-1/LiFSI system was almost constant regardless of lithium salt concentrations. Both polymer electrolytes showed high transference number of lithium ion: 0.57 for the poly-1/LiTFSI system and 0.56 for the poly-1/LiFSI system, respectively. The polymer electrolytes for the poly-1/LiTFSI system were thermally more stable than those for the poly-1/LiFSI system.     

Electrosynthesis and characterization of poly aniline/garnet nanoparticles for high-performance electrochemical capacitors

In this work, supercapacitive performance of polyaniline/yttrium aluminum garnet (YAG: Y₃Al₅O₁₂) nanoparticles (PANI/YAGNPs) was studied. YAG nanoparticles were synthesized by pulse electro-deposition method and after that, PANI/YAGNPs electrodeposited on the surface of glassy carbon electrodes through cyclic voltammetry. Morphological studies show that YAG nanoparticles were distributed in the structure of PANI filaments uniformly. XRD and FTIR were used to perform a structural study of materials. Different electrochemical techniques such as cyclic voltammetry (CV), galvano static charge discharge (CD), and impedance spectroscopy (EIS) were used to evaluate the applicability of using PANI/YAGNPs as an active material for supercapacitors. The specific capacitance (SC) of PANI and PANI YAG NPs electrodes calculated using CV technique are 240 and 440 F/g, respectively. Increasing the conductivity and stability of composite electrodes during continuous CD cycles compared to PANI ones are some features of using YAG NPs in the structure of polymer electrodes. Stability of composite electrodes remains about 98% through 1000 continuous cycles whereas the polymeric electrode loses about 91% of its capacitance during this time range.     

Synthesis, characterization and electrochemical properties of poly(methyl methacrylate)-grafted-poly(vinylidene fluoride-hexafluoropropylene) gel electrolytes

A new comb-like copolymer, poly(vinylidene fluoride-co-hexafluoropropylene)-g-poly(methyl methacrylate), or [P(VDF-HFP)-g-PMMA], was successfully synthesized through grafting in situ formed PMMA to the P(VDF-HFP) backbone. The composition of the P(VDF-HFP)-g-PMMA copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA) and elemental analysis. X-Ray diffractometry (XRD) and differential scanning calorimetry (DSC) were used to examine the reduction in crystallinity of P(VDF-HFP) due to the anchoring of PMMA segments on it. Gel electrolyte membranes based on the resulting copolymer were prepared by the Bellcore process. The ionic conductivity of Li⁺ across the membranes and the related transference number were measured. A study of the interfacial stability between Li electrode and the P(VDF-HFP)-g-PMMA gel electrolyte was also conducted to evaluate the suitability of the P(VDF-HFP)-g-PMMA copolymer in rechargeable lithium and lithium-ion battery applications.     

Preparation of poly(2-ethyl aniline)/kaolinite composite materials and investigation of their properties

Conductive poly(2-ethyl aniline) (PEAn)/kaolinite composite was prepared by chemical polymerization in aqueous HCl medium in the presence of kaolinite particles by using potassium chromate (K₂CrO₄) as oxidant. Effects of polymerization conditions, such as concentrations of oxidant and 2-ethyl aniline, polymerization time and temperature on PEAn content and conductivity of composite, were investigated. The prepared composite material, having the highest PEAn content and conductivity, was obtained in the polymerization carried out at 20 °C for 2 h with 0.2 M K₂CrO₄ and 0.2 M EAn. It was observed that the micro-hardness of prepared composites increased with the increase in the PEAn contents of composites. The highest micro-hardness value of 7.92 kg mm⁻² was reached at 24.6% PEAn content. Characterization of composites was carried out by FTIR spectroscopy, XRD, TGA and SEM techniques.     

Electrical and electrochemical properties of poly (methyl methacrylate) based nanocomposite gel electrolytes dispersed with dedoped (insulating) polyaniline nanofibers

In this work, we have investigated the effect of dedoped (insulating) polyaniline (PAni) nanofibers on the electrical and electrochemical properties of poly(methyl methacrylate) (PMMA)-based gel electrolytes. PAni nanofibers have been synthesized using interfacial polymerization technique. By analysis of X-ray diffraction (XRD) and impedance spectroscopy results, it has been demonstrated that the incorporation of dedoped PAni nanofibers up to a moderate concentration (4 wt%) to PMMA–(PC?+?DEC)–LiClO₄ gel polymer electrolyte system significantly enhances the ionic conductivity of the electrolyte system, which can be attributed to the inhibition of polymer chain reorganization upon dispersion of high aspect ratio nanofibers in PMMA matrix resulting in reduction in polymer crystallinity, which gives rise to an increase in ionic conductivity. At higher concentration, dedoped nanofibers appear to get phase separated and form insulating clusters, which impede ionic transport. The phase separation phenomena at higher fraction of nanofibers are confirmed by XRD. Studies on electrochemical behavior reveal that electrochemical potential window increases with the increase of nanofibers loading.     

The physical and electrochemical properties of poly(vinylidene chloride-co-acrylonitrile)-based polymer electrolytes prepared with different plasticizers

Lithium ion-conducting membranes with poly(ethylene oxide) (PEO)/poly(vinylidene chloride-co-acrylonitrile) (PVdC-co-AN)/lithium perchlorate (LiClO₄) were prepared by solution casting method. Different plasticizers ethylene carbonate (EC), propylene carbonate (PC), gamma butyrolactone (gBL), diethyl carbonate (DEC), dimethyl carbonate (DMC), and dibutyl phthalate (DBP) were complexed with the fixed ratio of PEO/PVdC-co-AN/LiClO₄. The preparation and physical and electrochemical properties of the gel polymer electrolytes have been briefly elucidated in this paper. The maximum ionic conductivity value computed from the ac impedance spectroscopy is found to be 3?×?10^?4 S cm^?1 for the EC-based system. From DBP-based system down to EC-based system, a decrease of crystallinity and an increase of amorphousity are depicted by X-ray diffraction technique, the decrease of band gap energy is picturized through UV–visible analysis, the decrease of glass transition temperature is perceived from differential scanning calorimetry plots, and the reduction of photoluminescence intensity is described through photoluminescence spectroscopy study at an excitation wavelength of 280 nm. Atomic force microscopic images of EC-based polymer electrolyte film show the escalation of micropores. Fourier transform infrared spectroscopy study supports the complex formation and the interaction between the polymers, salt, and plasticizer. The maximum thermal stability is obtained from thermogravimetry/differential thermal analysis, which is found to be 222 °C for the sample complexed with EC. The cyclic voltagram of the sample having a maximum ionic conductivity shows a small redox current at the anode, and cathode and the chemical stability is confirmed by linear sweep voltammetry.     

Studies on the electrochemical and dopamine sensing properties of AgNP-modified carboxylated cellulose nanocrystal-doped poly(3,4-ethylenedioxythiophene)

Ionics - Carboxylated cellulose nanocrystals (CNCC) were synthesized by treating microcrystalline cellulose with ammonium persulfate. Silver nanoparticles (AgNPs) were prepared on the surface of...     

Novel Chiral Conducting Poly[N-(9-Fluorenylmethoxycarbonyl)-L-Alanine] (PN9FA) with Good Fluorescence Properties via Electropolymerization

Poly[N-(9-fluorenylmethoxycarbonyl)-L-alanine] (PN9FA) films with good fluorescence properties and chirality were prepared electrochemically by direct anodic oxidation of N-(9-fluorenylmethoxycarbonyl)-L-alanine (N9FA) in boron trifluoride diethyletherate (BFEE). Results of FT-IR spectral measurements indicated that N9FA was probably polymerized through the coupling at the C (2) and C (7) positions. Results of electrochemical measurements of PN9FA showed good redox activity and stability. The fluorescence spectra indicated that PN9FA films were blue-light emitters. In addition, the structures and properties of the monomer and the polymers were characterized and evaluated with cyclic voltammograms (CVs), 1H-NMR, UV–vis spectra (UV), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM).     

Electro-optical properties of poly(2-ethynyl-N-hexylpyridinium bromide) and poly(2-ethynyl-N-hexylpyridinium iodide)

Poly(2-ethynyl-N-hexylpyridinium bromide) and poly(2-ethynyl-N-hexylpyridinium iodide) were synthesized by the direct polymerization of 2-ethynylpyridine and the corresponding n-hexyl halides without any additional initiator or catalyst under mild reaction condition. The polymerization proceeded well to give high yield of polymer. The polymer structures were characterized to have the conjugated polymer backbone system having N-hexylpyridyl moieties. The photoluminescence spectra of poly(2-ethynyl-N-hexylpyridinium bromide) and poly(2-ethynyl-N-hexylpyridinium iodide) showed that the photoluminescence peaks are located at 603 and 611 nm corresponding to the photon energy of 2.06 and 2.03 eV, respectively. The electrochemical properties of the resulting polymers were also measured and discussed.     

Phase transition studies in polymesomorphic compounds(v): Density studies in N-(p-n-Octyloxy benzylidene)-p-n-butyl aniline

The density, ρ, of N-(p-n-octyloxy benzylidene) p-n-butyl aniline (OBBA) is measured as a function of temperature from the isotropic liquid to the smectic-G phase. The compound is trimorphic, exhibiting three smectic phases, smectic-G, crystal smectic-B, and smectic-A phase. The changes in density across the phase transformations and the calculated thermal expansion coefficients confirm the order of the transitions as first order. Particular importance of the smectic-A to crystal smectic-B transformation, which is of first order, is apparent from the density jump across the transition.     

Synthesis and spectral-luminescent properties of poly(N-isopropylacrylamide)

The spectral-luminescent characteristics of water and methanol solutions of polymers containing tetraphenylporphyrin substituents were investigated. The water-soluble polymer was obtained by the interaction of poly(N-isopropylamide) containing N-oxysuccinimide substituents with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin. From the synthesized polymer its analog with Zn-porphyrin substituents was obtained. This phenomenon is attributed to the specific features of the conformational behavior of polymeric chains in water solutions. Water solutions of polymers experience a thermally reversible phase transition upon heating, which is accompanied by a considerable enhancement of light scattering. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 483–487, July–August, 2000.     

Phase transition studies in polymesomorphic compounds (ii): Ultrasonic velocity studies in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline

The variation of ultrasonic velocity in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline with temperature in the isotropic, nematic, S_A S_B and S_G phases is measured. All the phase transitions are of first order. The adiabatic compressibility β _ad , molar sound veclocity or Rao number R_n , and molar compressibility or Wada constant A are computed. Molar sound velocity and molar compressibility of HBBA are compared with the values of other compounds. They are found to be in good agreement with theory.     

Conformational properties of poly(p-Phenylene vinylene)

We investigate the quasiparticle conformational defects (excitons, polarons and bioplarons) in the phenylene vinylene oligomers. The conformations are determined by means of the minimization of the total Hartree-Fock energy calculated at 3–21G level. The infrared vibrational transitions are calculated and the types of vibrations are assigned. The theoretical spectra are in good agreement with the experimental vibrational spectrum of poly(p-phenylene vinylene). Presented at the Czech-Israeli-German Symposium “Dynamical Processes in Condensed Molecular Systems”, Prague, Czech Republic, 26–30 May 1997. The quantum mechanical calculations were performed on the following computers: Power Challenge XL at Prague Supercomputing Centre, Charles University, IBM Power 2 at Supercomputing Centre of the Czech Technical University and Power Challenge XL at Supercomputing Centre Brno. The work is supported by Projects No. 202/94/0453 and 202/97/1016 of the Grant Agency of the Czech Republic and by Project No. 155/96 of the Grant Agency of the Charles University.     

Magnetic properties of poly(3-hexylthiophene)

A room temperature ferromagnetic phase is observed in samples of poly(3-hexylthiophene) partially doped with ClO₄⁻. The magnetic behavior presents a strong dependence on the sample preparation conditions, in particular, a dependence with the final potential of the sample after reduction. The origin of the ferromagnetism is proposed to be associated with interactions between spin 1/2 polarons formed in the polymeric chain upon doping. The dependence of saturation and spontaneous magnetization as the function of the final potential after reduction shows a way to control the magnetic properties of this polymer.     

Electronic properties of polyquinolines and poly(2,6-naphthylene)

We present a Valence Effective Hamiltonian (VEH) study of the electronic properties of polyquinoline, poly(4-phenylquinoline), and poly(2,6-naphthylene). Parameters important with redard to the conductivity properties upon doping, such as ionization potentials, bandwidths, and bandgaps, are obtained from the band structures of the title compounds. Results indicate that these polymers have : (i) large ionization potentials (so that fairly strong acceptors are required for effective p-type doping); (ii) large electron affinities (as a result, n-type doping is feasible); and (iii) quite small bandwidths. This is consistent with the relatively low conductivities reported so far for the doped polymers.     

Ionic conductivity and electrochemical stability of poly(methylmethacrylate)-poly(ethylene oxide) blend-ceramic fillers composites

The role of inorganic ceramic fillers namely nanosized Al₂O₃ (15-25 nm) and TiO₂ (10-14 nm) and ferroelectric filler SrBi₄Ti₄O₁₅ (SBT CIT) (0.5 μm) synthesized by citrate gel technique (CIT) on the ionic conductivity and electrochemical properties of polymer blend 15 wt% PMMA+PEO₈:LiClO₄+2 wt% EC/PC electrolytes were investigated. Enhancement in conductivity was obtained with a maximum of 0.72×10⁻⁵ S cm⁻¹ at 21 °C for 2 wt% of SrBi₄Ti₄O₁₅ (SBT CIT) composite polymer electrolyte. The lithium-ion transport number and the electrochemical stability of the composite polymer electrolytes at ambient temperature were analyzed. An enhancement in electrochemical stability was observed for polymer composites containing 2 wt% of SrBi₄Ti₄O₁₅ (SBT CIT) as fillers.     

Peroxomonosulphate initiated graft copolymerization of aniline onto poly(propylene) fibre - A kinetic approach

Graft copolymerization of poly(aniline) (PANI) onto poly(propylene) (PP) fibre was carried out in aqueous acidic medium under nitrogen atmosphere by using peroxomonosulphate (PMS) as a lone initiator. The non-conducting fibre was now made into a conducting one through the chemical grafting of PANI units onto the PP fibre backbone. The content of PANI in the backbone was found to vary while varying the [ANI], [PMS] and amount of PP fibre. Various graft parameters were evaluated. The chemical grafting of PANI onto PP fibre was confirmed by conductivity measurements.