Exploration of the formation mechanisms of polyaniline nanotubes and nanofibers through a template-free method

This study reports the polymerization of aniline monomers in different HCl concentrations to investigate the formation mechanisms of one-dimensional polyaniline (PANI) nanostructures. Fourier transform infrared (FT-IR) spectra indicate that the products obtained in different acidic solutions have different molecular structures. In low-acidity conditions (HCl concentration ≤0.1 M), aniline monomers form phenazine-like aniline units in the initial reaction stage. As the reaction continues, a structure consisting of a head of phenazine-like aniline units and a tail of para-linked aniline units develops. By contrast, the reaction only produces para-linked aniline units as the concentration of HCl increases to 0.2 M. PANI products with different molecular structures exhibit different shapes, including nanotubes and nanofibers. For nanotubes, electron microscopy images reveal the flake-like intermediates formed in the initial reaction stage and then curl into nanotubes as the reaction proceeds. The phenazine-like aniline units serve as the axis for PANI nanotube curling. On the other hand, the para-linked aniline units act as a template for the formation of PANI nanofibers. This study demonstrates the formation mechanisms of PANI nanotubes and nanofibers. The acid concentration in the polymerization solution is the critical factor determining whether the aniline monomers form nanotubes or nanofibers.     

Preparation and characterization of polyaniline nanoparticles synthesized from DBSA micellar solution

Chemical oxidative polymerization of aniline was performed in a micellar solution of dodecylbenzene sulfonic acid (DBSA, anionic surfactant) to obtain conductive nanoparticles with enhanced thermal stability and processability. DBSA was used to play both the roles of surfactant and dopant. The polymerization kinetics and optimum polymerization conditions were determined by UV–VIS spectra. The optimum molar ratio of oxidant to aniline was 0.5 and DBSA content was the most important factor in the formation of polyaniline (PANI) salt. The polymerization rate was increased with increasing DBSA concentration. The reaction model was proposed on the basis of the roles of DBSA. The electrical conductivity varied with the molar ratio of DBSA to aniline and the highest conductivity of particles was 24 S/cm. The layered structure due to PANI backbone separated by long alkyl chains of DBSA was observed and it seems to facilitate the electrical conduction. The doping level of particle was fairly high and was dependent on the preparative conditions. The average size of the PANI particles determined by Guinier plot of small-angle X-ray scattering (SAXS) measurement was 20–30 nm, which was well coincidence with scanning electron microscopy (SEM) results     

Polyaniline nanofibers synthesized by rapid mixing polymerization

Polyaniline (PANI) nanofibers were chemically synthesized by a rapid mixing polymerization with aniline concentration of 0.5 M. The time needed for the formation of PANI in the reaction medium decreased with increase of the molar ratio of ammonium peroxydisulphate (APS)/aniline and temperature. Morphological study showed at the end of polymerization, only the ones prepared with low molar ratio of APS/aniline (e.g. 0.25 and 0.50) and temperature (e.g. 0 and 20 °C) are nanofibers with diameters of ∼50 nm, though the initially formed products are all nanofibers, while with increasing of molar ratio of APS/aniline to 1 and temperature to 20 °C or higher, agglomerates of PANI nanofibers with diameters of ∼100 nm and larger sized irregular particles were formed. The yield of PANI nanofibers was in the range of 13.4–42.3%, which is favorable for mass production of PANI nanofibers. Conductivity measurement, UV–vis and FTIR spectra were performed to characterize the products. The conductivity of the PANI nanofibers increased with molar ratio of APS/aniline at low temperature, while decreased at higher temperature, which might be resulted from the degradation of PANI molecules in the presence of more APS molecules at higher temperature.     

Self-assembled polyaniline nanotubes and nanoribbons/titanium dioxide nanocomposites

Self-assembled polyaniline (PANI) nanotubes, accompanied with nanoribbons, were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous medium, in the presence of colloidal titanium dioxide (TiO₂) nanoparticles of 4.5 nm size, without added acid. The morphology, structure, and physicochemical properties of the PANI/TiO₂ nanocomposites, prepared at various initial aniline/TiO₂ mole ratios, were studied by scanning (SEM) and transmission (TEM) electron microscopies, FTIR, Raman and inductively coupled plasma optical emission (ICP-OES) spectroscopies, elemental analysis, X-ray powder diffraction (XRPD), conductivity measurements, and thermogravimetric analysis (TGA). The electrical conductivity of PANI/TiO₂ nanocomposites increases in the range 3.8 × 10^?4 to 1.1 × 10^?3 S cm^?1 by increasing aniline/TiO₂ mole ratio from 1 to 10. The morphology of PANI/TiO₂ nanocomposites significantly depends on the initial aniline/TiO₂ mole ratio. In the morphology of the nanocomposite synthesized using aniline/TiO₂ mole ratio 10, nanotubes accompanied with nanosheets prevail. The nanocomposite synthesized at aniline/TiO₂ mole ratio 5 consists of the network of nanotubes (an outer diameter 30–40 nm, an inner diameter 4–7 nm) and nanorods (diameter 50–90 nm), accompanied with nanoribbons (a thickness, width, and length in the range of 50–70 nm, 160–350 nm, and ～1–3 μm, respectively). The PANI/TiO₂ nanocomposite synthesized at aniline/TiO₂ mole ratio 2 contains polyhedral submicrometre particles accompanied with nanotubes, while the nanocomposite prepared at aniline/TiO₂ mole ratio 1 consists of agglomerated nanofibers, submicrometre and nanoparticles. The presence of emeraldine salt form of PANI, linear and branched PANI chains, and phenazine units in PANI/TiO₂ nanocomposites was proved by FTIR and Raman spectroscopies. The improved thermal stability of PANI matrix in all PANI/TiO₂ nanocomposites was observed.     

Ionic liquid-induced formation of polyaniline nanostructures during the chemical polymerization of aniline in an acidic aqueous medium

Nanostructured polyanilines (PANIs) with a variety of morphologies were synthesized in acidic aqueous solutions with an added ionic liquid, 1-butyl-3-methylimidazolium chloride. The influence of various reaction conditions, i.e., the molar ratio of aniline to ionic liquid and initial aniline concentration, on the morphology and properties of the synthesized PANIs were investigated. The morphologies of the PANIs, as studied by scanning electron microscopy (SEM), range from nanowires to complex three-dimensional structures and were influenced particularly by the molar ratio of aniline to ionic liquid. The chemical structure and molecular-weight characteristics, as determined by Fourier-transform infrared spectroscopy (FTIR), UV–Vis spectroscopy and size-exclusion chromatography (SEC), were not affected by the reaction conditions, indicating that the aniline polymerization mechanism did not change in the presence of the ionic liquid, which acted as a soft template. The conductivities of the prepared PANI samples, as measured by impedance spectroscopy, were of the order of 10^?2 S/cm.     

Synthesis of PANI nanostructures with various morphologies from fibers to micromats to disks doped with salicylic acid

Shape-controllable polyaniline (PANI) nanostructures varying from fibers to micromats and disks were synthesized via a self-assembly process with salicylic acid (SA) as dopant. It has been achieved just by tuning the concentration of aniline, the mole ratio of SA to aniline, and the mole ratio of APS to aniline in the same reaction. The diameters of the fibers could be controlled from 30 to 400 nm by adjusting the concentration of aniline. Micromats of fibers would be formed by changing the mole ratio of SA to aniline. Disk-like PANI nanostructures were synthesized when decreasing the mole ratio of APS to aniline. Scanning electron microscopy and transmission electron microscopy were applied to investigate various kinds of morphologies. The mechanism of forming these morphologies was proposed to be adjusted by the pH value during polymerization. Ultraviolet–visible (UV–vis) absorption spectra and Raman spectra suggested that these as-prepared PANI were in conductive emeraldine state and featured obviously different molecular structures, which aroused from different reaction conditions.     

Chiral polyaniline with flaky, spherical and urchin-like morphologies synthesized in the l-phenylalanine saturated solutions

Chiral polyaniline (PANI), of flaky, spherical and urchin-like morphologies, was synthesized in the saturated l-phenylalanine solution by adjusting the molar ratio of l-phenylalanine to aniline from 0.25 to 40. The concentration of l-phenylalanine solution was constant, which was different from the conventional synthesis. The morphologies of PANI were observed by scanning electron microscopy. The molar ratio of l-phenylalanine to aniline and the amount of aniline were proposed to be crucial to the morphologies. Circular dichroism spectra confirmed that l-phenylalanine endowed predominately one type of chirality to polyaniline by hydrogen bonding. The optical, structural and electrochemical properties of these synthesized PANI were characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy and cyclic voltammetry, respectively. There were some insulating structures, such as oligomers, in the PANI chains, which were caused by the weak acid circumstance during the polymerization.     

Synthesis and properties of high performance nanostructured polyaniline: Effect of initiator dosage and molecular oxygen

The effects of ammonium persulfate (APS)/aniline feed molar ratio or O₂ bubbling on the polymerization of polyaniline (PANI) in self-stabilized dispersion polymerization (SSDP) were examined. As the APS/aniline feed molar ratio was increased from 0.25/1.00 to 1.50/2.00, the polymerization yield was enhanced from 20% to 80%. However the molecular weight reduction with increased feed ratio, that is normally observed when PANI was polymerized in aqueous medium, was little. The O₂ bubbling during polymerization made the nanostructure of PANI to be finer, and this improved the solubility of PANI in solvent. The FT-IR spectra showed that the PANI prepared by SSDP, which have high conductivity in the range of 600–800 S/cm, contained less amount of the structures by ortho-coupling or Michael reductive addition of aniline compared to that synthesized by the standard method in an aqueous medium.     

A new approach for the synthesis of polyaniline microstructures with a unique tetragonal star-like morphology

Shape-controllable polyaniline (PANI) microstructures with a unique tetragonal star-like morphology were synthesized by a rapid initiated strategy with glycine (Gly) as dopant. The results demonstrate that the morphology of PANI microstructures is significantly influenced by the molar ratio of aniline to glycine. The PANI prepared in this study exhibits nanofiber-like morphology with exceptionally high crystallinity. These nanofibers can self-assemble into tetragonal star-like microstructures with a unique alignment. The chemistry, morphology, and crystal structure of glycine doped star-like microstructures were studied using SEM, UV–vis, FT-IR, XRD and cyclic voltammetry (CV).     

SERS,FT-IR and photoluminescence studies on single-walled carbon nanotubes/conducting polymers composites

Surface-enhanced Raman scattering (SERS), Fourier transform infrared (FT-IR) and photoluminescence (PL) spectroscopies were used to investigate composites based on single-walled carbon nanotubes (SWNTs) and different conducting polymers like polyaniline (PANI), poly-paraphenylene vinylene (PPV) and poly 3-hexylthiophene (3-PHT). In the case of SWNTs/PANI, different composites are obtained by adding dispersed SWNTs powder to the polymer solutions and by chemical polymerization of aniline in presence of SWNTs. The difference originates in the irreversible chemical transformation of SWNTs in the polymerization medium. The synthesis medium used for the preparation of PANI transforms SWNTs in fragments of shorter length like closed-shell fullerenes. This explains the similarity of SERS and FT-IR spectra of the composites PANI/SWNTs and PANI/C₆₀, chemically synthesized. Electrochemical polymerization of aniline in an HCl solution on a SWNT film leads to a covalent functionalization of SWNTs with PANI. In this case, Raman scattering data suggest an additional nanotubes roping with PANI as a binding agent. A post treatment with the NH₄OH solution of polymer-functionalized SWNTs involves an internal redox reaction between PANI and carbon nanotubes. As a result, the polymer chain undergoes a transition from the semi-oxidized state into a reduced one. In the case of PPV and 3-PHT, the effect of the concentration of SWNTs on the photoluminescence properties will be described and compared, as probes of interaction.     

Carbon nanotube/polyaniline core-shell nanowires prepared by in situ inverse microemulsion

By the in situ inverse microemulsion, we prepared multi-walled carbon nanotubes/polyaniline composites (MWNTs/PANI). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. Fourier transform infrared (FT-IR) spectra suggested that the π-bonded surface of the carbon nanotubes (CNTs) interact strongly with the conjugated structure of the PANI shell layer. The thermal stability and electrical conductivity of the MWNTs/PANI composites were examined by thermogravimetric analysis (TGA) and conventional four-probe method. In comparison with the pure PANI, the decomposition temperature of the MWNTs/PANI (1 wt% MWNTs) composites increased from 360 to 400 °C and the electrical conductivity of MWNTs/PANI (1 wt% MWNTs) composites was increased by one order of magnitude.     

Template synthesis of polyaniline in the presence of phosphomannan

The synthesis of a water-soluble and conducting polyaniline (PANI)–phosphomannan (PMa) complex is presented. Chemical polymerization of aniline was carried out in the presence of PMa, a novel polymeric phosphoric acid and a kind of biomaterial. It was found that the extent of polymerization was affected greatly by initial molar ratio of aniline to PMa in reaction media. A water-soluble and conducting PANI–PMa complex has been obtained under suitable conditions and it exhibited a maximum conductivity by appropriate control of molar ratio of aniline to PMa. The synthesized PANI was characterized by UV–VIS, Fourier transform infrared spectrometer (FT-IR), thermogravimetric analysis (TGA) and inherent viscosity. TGA showed that PANI–PMa complex has highly thermal stability, which was also confirmed by conductivity measurement after exposing the casting films at high temperature.     

Polyaniline composite by in situ polymerization on a swollen PVA gel

Interpenetrating polyaniline (PANI) formation in a 3D network of poly(vinyl alcohol) (PVA) hydrogel was developed. Polymerization was effected by immersing swollen PVA hydrogel previously soaked with ammonium persulfate (APS) in 1 M HCl solution of aniline hydrochloride (AnHCl). Gradual transformation of the swollen gel from colorless transparent gel to an opaque green color indicated the formation of PANI emeraldine salt (ES) on the surface and bulk of the PVA gel matrix. Characterization by UV–vis spectra, ATR-FTIR spectra and X-ray diffraction analyses supported the formation of PANI–PVA composite film. The surface morphology of the film was studied by FESEM. Electrical conductivity of the film was measured by four-probe method.     

Preparation,FTIR spectroscopic characterization and isothermal stability of differently doped conductive fibers based on polyaniline and polyacrylonitrile

Conductive fibers based on polyaniline (PANI) and polyacrylonitrile (PAN) were obtained by stirring with magnetic bar. This research was conducted to investigate conducting fibers of polyaniline:polyacrylonitrile (PANI:PAN) composite with different weight ratios of aniline in PAN matrix. The fibers were prepared by stirring process. The best conductivity behavior of the fibers was obtained with 5 mL of aniline. The fibers obtained were characterized using Fourier-transform infrared spectra (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The variation of electrical conductivity with different type doping agents (HCl, H₂SO₄ and HClO₄) and the stability in terms of DC electrical conductivity retention was studied in an oxidative environment by isothermal characteristics.     

In situ synthesis and characterization of polyaniline–CaCu3Ti4O12 nanocrystal composites

High dielectric constant (ca. 2.4 × 10⁶ at 1 kHz) nanocomposite of polyaniline (PANI)/CaCu₃Ti₄O₁₂ (CCTO) was synthesized using a simple procedure involving in situ polymerization of aniline in dil. HCl. The PANI and the composite were subjected to X-ray diffraction, Fourier transform infrared, thermo gravimetric, scanning electron microscopy and transmission electron microscopy analyses. The presence of the nanocrystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. Frequency dependent characteristics of the dielectric constant, dielectric loss and AC conductivity were studied for the PANI and the composites. The dielectric constant increased as the CCTO content increased in PANI but decreased with increasing frequency (100 Hz–1 MHz) of measurement. The dielectric loss was two times less than the value obtained for pure PANI around 100 Hz. The AC conductivity increased slightly up to 2 kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers.     

Self-assembled polyaniline 12-tungstophosphate micro/nanostructures

Polyaniline (PANI) micro/nanostructures were synthesized by the external-template-free oxidative polymerization of aniline in aqueous solution of 12-tungstophosphoric acid (WPA), using ammonium peroxydisulfate (APS) as an oxidant and starting the oxidation of aniline from slightly acidic media (pH 5.4–5.9). The effect of the initial weight ratio of WPA to aniline on molecular structure, morphology, and physicochemical properties of polyaniline 12-tungstophosphate (PANI-WPA) was investigated by FTIR, Raman and inductively coupled plasma optical emission (ICP-OES) spectroscopies, elemental analysis, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and conductivity measurements. The morphological change of polymerization products during a single polymerization process, from non-conducting submicro-/microspherical oligoaniline intermediates to semiconducting PANI-WPA consisted of self-assembled nanotubes and/or nanorods co-existing with submicro-/microspheres, has been revealed by SEM and TEM. The average diameter of nanorods in PANI-WPA samples decreased with increasing the initial WPA/aniline weight ratio. The incorporation of 12-tungstophosphate counter-ions into PANI matrix has been proved by FTIR, Raman and ICP-OES spectroscopies, TGA and DTA analysis. Electrical conductivity of PANI-WPA increased in the range (2.5–5.3) × 10^?3 S cm^?1 with the increase of the initial WPA/aniline weight ratio. The presence of branched structures and phenazine units besides the ordinary paramagnetic and diamagnetic emeraldine salt structural features in PANI-WPA was proved by FTIR and Raman spectroscopies.     

Synthesis and characterization of polyaniline nanoparticles in SDS micellar solutions

Polyaniline (PANI) dispersions consisting of 10–20 nm sized nanoparticles were prepared by oxidation with ammonium peroxydisulfate (APS) in sodium dodecylsulfate (SDS) micellar solutions. Coalescence and coagulation were prevented by electrostatic repulsive interaction between anionic SDS micelles. Particle morphology was dependent on the initial shape of surfactant aggregates (micelles) and the molar ratio of SDS to aniline monomer. Spherical particles were obtained at very low monomer concentration and the shape of particles began to be distorted from the spherical shape as monomer concentration increased at constant 0.2 M SDS concentration. The size of spherical particles was the same order of the micellar size or slightly larger. UV–VIS spectroscopy, compositions of PANI powder, morphology, crystalline structure, thermal stability, molecular weight and conductivity of PANI particles synthesized at various monomer and surfactant concentrations were investigated.     

Blends of HCl-doped polyaniline nanoparticles and poly(vinyl chloride) with extremely low percolation threshold — a morphology study

Blends of hydrochloric acid-doped polyaniline (PANI·HCl) nanoparticles and poly(vinyl chloride) (PVC) have been prepared by redispersing sedimented colloidal particles of PANI in tetrahydrofuran solutions of PVC using ultrasound and casting the film from the dispersion. The blends have the characteristics of extremely low percolation threshold at a volume fraction of PANI of 4.02 × 10⁻⁴. The morphology of the blends as revealed by transmission electron microscopy (TEM) of the blend films directly cast on TEM grids is discussed. Above the percolation threshold the dispersed PANI·HCl phase shows a globular network morphology in contrast to the fibrillar network morphology observed earlier for PANI·HCl-poly(vinyl alcohol) blends prepared by the present method.     

In situ self-organization of carbon black–polyaniline composites from nanospheres to nanorods: Synthesis, morphology, structure and electrical conductivity

Nanostructured composites of polyaniline (PANI) with carbon black (CB) were synthesized by an in situ self-organization process. The synthesis is based on the polymerization of aniline in a micellar solution of p-toluenesulfonic acid (TSA) with different weight percentages of CB using ammonium peroxydisulfate (APS) as the oxidizing agent. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), UV–vis spectroscopy, and the four-probe meter were used to study the morphological, structural, thermal, and electrical properties of CB–PANI nanocomposites. The results demonstrate that the morphology, thermal stability, and electrical conductivity of the nanocomposites were significantly influenced by the content of CB. SEM results reveal that there was a transition in morphology from composite nanospheres to one-dimensional (1D) composite long nanorods with an increase of CB content. XRD and UV–vis spectra results revealed that there was an increase in the crystallinity and a shift of quinoid transition bands towards lower wavelengths as the amount of CB in the composite increased. The mechanism for the formation of nanostructured composites was explained on the basis of the self-organization of micelles. CB–PANI nanocomposites with a maximum electrical conductivity of 1.38 S/cm were obtained; this is at least three orders of magnitude higher than that of pristine PANI.     

Uniform polyaniline microspheres: A novel adsorbent for dye removal from aqueous solution

Uniform polyaniline (PANI) microspheres were synthesized by a facile polymerization of aniline monomer in the acidic medium. The structure and morphology of PANI microspheres were characterized by means of FTIR spectrometer, X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). Adsorption characteristics of PANI microspheres were examined using methyl orange (MO) as adsorbate. Batch adsorption experiments were carried out to investigate adsorption kinetics and isotherms of PANI microspheres. Adsorption equilibrium studies showed that MO adsorption followed Freundlich model. The adsorption kinetics was best described by pseudo-second-order model. The results indicated that PANI microspheres can be used as a novel, effective and low-cost adsorbent material for dye removal.