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.     

Electrically conducting nylon 6,6–polyaniline short composite fibres synthesised by the solvent coagulation method

Polyaniline (PANI) was blended with nylon 6,6 in concentrated H₂SO₄ and HCl solutions. The solvent coagulation method was utilised to extract short composite fibres of a centimetre in length. A solution of n-butyl acetate, acetone, toluene, 1 μM HCl and chloroform were used as coagulating bath to extract the fibres. The diameters of the fibres ranged from 200 to 300 nm, while the length measured approximately 1 cm, as determined from Scanning Electron Microscopy (SEM). The electrical conductivity varied from 10⁻⁴ to 10⁻² S/cm for different mass fractions of PANI (x_PANI) in the composite fibres. The percolation threshold was reached at x_PANI values between 0.15 and 0.2, and further addition of PANI resulted in saturation of the conductivity of the composite fibre. To observe the effect of MWCNTs on the electrical conductivity of the nylon–PANI fibres, 0.04 g, 0.08 g, 0.4 g and 0.5 g of MWCNTs (1, 2, 10, 12.5 weight percentage, respectively) were added into the nylon–PANI solution and were extracted as fibres in the aforementioned solvents. The electrical conductivity of the short fibres increased by an order of magnitude (0.372 S/cm at 12.5 wt.%) when they were extracted in the presence of the MWCNTs. PANI doped in concentrated HCl exhibited an electrical conductivity of 4.46 S/cm.     

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.     

Bridge effect of silver nanoparticles on electrochemical performance of graphite nanofiber/polyaniline for supercapacitor

In this work, silver (Ag) nanoparticles were deposited onto graphite nanofibers (GNFs) by chemical reduction while polyaniline-coated Ag-GNFs (Ag-GNFs/PANI) were prepared by in situ polymerization. The effect of the Ag nanoparticles intercalated in composite interface on the electrochemical performances, such as CV curve, charge–discharge behaviors, and specific capacitance of the GNFs/PANI was investigated. It was found that nano-sized Ag particles could be uniformly deposited onto the GNFs and that Ag-GNFs were successfully coated by PANI via in situ polymerization. According to the charge–discharge curves, the highest specific capacitance (212 F/g) of the Ag-GNFs/PANI was obtained at a scan rate of 0.1 A/g, as compared to 153 F/g for GNFs/PANI and 80 F/g for PANI. This indicated that the Ag nanoparticles that were deposited onto the GNFs led to a bridge effect between GNFs and PANI to improve the charge transfer, which resulted in the enhanced electrochemical performances of the composites due to a synergistic effect.     

Polyaniline nanofibers synthesized in compressed CO2

Polyaniline (PANI) nanofibers were synthesized in compressed liquid carbon dioxide without any template or surfactant. The polymerization of aniline took place at the interface between CO₂ and aqueous solution in a high-pressure stirred reactor. The prepared PANI nanofibers were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), electrical conductivity (EC), Fourier-transform infrared (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses. The yield of polymerization was high enough to reach 63.04% while maintaining small diameters of the PANI nanofibers. This result is very important for the preparation of the PANI nanofibers because no other previous investigations have achieved both high yield and small diameter of fibers at the same time. Through SEM and TEM analyses, we observed that the PANI nanofibers had diameter range of 30–70 nm and a length range of 0.3–1 μm, which caused them to disperse well in various solvents such as water, ethanol, 2-propanol, m-cresol and toluene. The electrical conductivity of the PANI nanofibers was 4.34 S/cm at 20 °C. The XRD diffraction pattern showed that the PANI nanofibers had crystalline one-dimensional structures, which gave high thermal stabilities as confirmed by TGA.     

In situ template polymerization of aniline on the surface of negatively charged TiO2 nanoparticles

The in situ oxidative template polymerization of aniline was performed successfully on the surface of negatively charged titania (TiO₂) nanoparticles with a mean diameter of 40 nm using ammonium persulfate and a Chem-Solv solution at pH 1 and 25 °C. SEM showed that the resulting polyaniline (PANI)/TiO₂ composites were well dispersed in solution due to the electrostatic repulsion force. Ultraviolet/visible spectroscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, and cyclic voltammetry showed that the optical, thermal, and electrical properties of PANI/TiO₂ composites were quite different from those of pure PANI or TiO₂, which was attributed to the strong interaction between the two components. The conductivity of the PANI/TiO₂ composite was estimated to be 0.91 × 10⁻¹ S/cm at 25 °C in the range of semiconductor.     

Conducting and magnetic behaviors of polyaniline coated multi-walled carbon nanotube composites containing monodispersed magnetite nanoparticles

High conductivity and supermagnetism of polyaniline (PANI)-coated multi-walled carbon nanotube (MWCNT) composites containing monodispersed 6 nm iron oxide (Fe₃O₄) nanoparticles has been successfully synthesized by in situ chemical oxidative polymerization using anionic surfactant dodecylbenzenesulfonic acid sodium salt. Hydrophilic 6 nm spherical Fe₃O₄ nanoparticles fabricated by the thermal decomposition process were chemically modified using 11-aminoundecanoic acid tetramethylammonium salt. The modified nanoparticles were further mixed with carboxylic acid containing multi-walled carbon nanotubes (c-MWCNTs) in an aqueous solution to form one-dimensional Fe₃O₄ coated c-MWCNT template and PANI/c-MWCNT nanocomposite were then synthesized via in situ chemical oxidative polymerization in HCl solution. Structural and morphological analysis using FESEM, HRTEM and XRD showed that the fabricated Fe₃O₄ coated c-MWCNT/PANI nanocomposites are one-dimensional core (Fe₃O₄ coated c-MWCNT)–shell (PANI) structures. The electrical conductivity of 1 wt% Fe₃O₄ coated c-MWCNT/PANI nanocomposites at room temperature is 37.7 S/cm, which is decreased to 28.6 S/cm with the loading of 5 wt% Fe₃O₄ nanoparticles. The magnetic properties of Fe₃O₄ coated c-MWCNT/PANI nanocomposites exhibit supermagnetism with saturation magnetization in the range of 0.04–0.15 emu/g, which increases as the amount of Fe₃O₄ nanoparticles increases.     

Preparation and characterization of polyindole nanofibers by electrospinning method

Polyindole nanofibers with diameter ranging from 770 nm to 250 nm were firstly fabricated by an electrospinning method. Chemically synthesized polyindole was dissolved in acetonitrile to make polymer solution under ultrasonification. Electrospinning of polyindole was then carried out under electrical field strength of 1.0 kV/cm. The electrospun polyindole nanofibers exhibited smooth surface and the diameter of the fibers was ranged from 768 nm to 255 nm. The specific surface areas of polyindole nanofibers were ranged from 32 to 65 m²/g, which is significantly higher than that of the powder with same volume. The electrical conductivity of the polyindole nanofibers can reach 0.24 S/cm, which is much higher than that of the polyindole film. The polyindole nanofibers showed high thermal stability with glass transition temperature (T_g) around 132 °C and melting point (T_m) around 239 °C. The crystallinity of polyindole nanofibers was higher than that of polyindole film due to the formation of ordered molecule chains during the electrospinning. Cyclic voltammetry test results revealed that the doping and de-doping processes of BF₄⁻ ions were reversible and polyindole nanofibers had high electronically activity in the electrolytic solution containing LiBF₄.     

Synthesis of polyaniline/NiO nanobelts by a self-assembly process

Polyaniline (PANI) nanotubes (∼180 nm in diameter) were synthesized in the presence of sodium dodecylbenzenesulfonate (SDBS) as a micellar template and dopant, whereas PANI/NiO nanobelts (300–700 nm in diameter) were obtained with the addition of NiO nanoparticles (∼10 nm in diameter). Results showed that the size of PANI/NiO composite nanobelts increased with an increase content of NiO nanoparticles. XRD, Fourier transform infrared (FTIR) and UV–vis spectroscopy were used to characterize the chemical structures of PANI nanotubes and PANI/NiO nanobelts. The thermal stability and conductivity of samples were affected by the content of NiO. The coordination bonds between NiO and aniline were the key factor that resulted in the morphological change of PANI.     

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.     

Fabrication of poly-3-hexylthiophene/polyethylene oxide nanofibers using electrospinning

P3HT–PEO blend nanofibers were produced by electrospinning from chloroform solutions. A morphological study was carried out as a function of the processing parameters as well as the ratio between the two polymers. The fibers containing at least 60 wt.% of P3HT presented striated surfaces that could be explained by the alignment of the polymer domains along the fiber axis. The structural arrangement of the polymers was found to vary according to the polymers relative contents. The maximum electrical conductivity found for unaligned mats was 0.16 S/cm and increased to 0.3 S/cm when the nanofibers were aligned along a preferential direction.     

Synthesis of polyaniline nanotubes using Mn2O3 nanofibers as oxidant and their ammonia sensing properties

In this work, a new method for the synthesis of polyaniline (PANI) nanotubes was presented. Experimentally, Mn₂O₃ nanofibers prepared by electrospinning technique were used as the oxidant template to initiate the polymerization of aniline in acid solution. After reaction, polyaniline shells were formed on the Mn₂O₃ nanofiber surface, and the Mn₂O₃ nanofibers were spontaneously removed. As a result, PANI nanotubes were obtained. As-prepared PANI nanotubes show an average diameter of 80 nm and inner diameter of 38 nm. The final PANI nanotubes were characterized by SEM, EDX, TEM, FTIR and XRD. The gas sensing of as-obtained PANI nanotubes was also investigated. It was found that the PANI nanotube sensing device could detect as low as 25 ppb NH₃ in air at room temperature with good reversibility.     

Synthesis of polyaniline nanostructures via soft template of sucrose octaacetate

Highly crystallized polyaniline (PANI) nanostructures were polymerized by oxidative polymerization in the presence of sucrose octaacetate acting as an in situ seed and a soft template, and ammonium peroxydisulfate (APS) acting as an oxidizing agent. PANI nanofibers and nanorods were obtained using 2 and 3 g sucrose octaacetate, respectively. The nanostructures containing irregular-shaped agglomerates, such as particulate particles and scaffolds were observed with increasing the concentrations of sucrose octaacetate. The polymerized PANI was characterized using Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetry analysis (TGA). Results showed that the presence of sucrose octaacetate during polymerization could only induce a change in morphology, but could not influence the molecular structure of the resulting PANI. Compared with those derived with 1, 3, and 4 g sucrose octaacetate, the polymerized PANI from 2 g sucrose octaacetate possessed higher thermal stability and electrical conductivity due to its higher crystallinity and highly ordered structure. A mechanism for the formation of PANI nanostructures is also proposed.     

Facile synthesis of polyaniline nanofibers using pseudo-high dilution technique

A new approach for the synthesis of polyaniline nanofibers under pseudo-high dilute conditions in aqueous system has been developed. High yield nanoscale polyaniline fibers with 18–110 nm in diameter are readily prepared by a high aniline concentration 0.4 M oxidation polymerization using ammonium persulfate (APS) as an oxidant in the presence of hydrochloric acid (HCl), perchloric acid (HClO₄), (1S)-(+)-10-camphorsulfonic acid (CSA), acidic phosphate PAEG120 (PA120) and sulfuric acid (H₂SO₄) as the dopants. The novel pathway always produces polyaniline nanofibers of tunable diameters, high conductivity (from 10⁰ to 10¹ S/cm) and crystallinity.     

Synthesis of highly conductive poly(3,4-ethylenedioxythiophene) fiber by simple chemical polymerization

Poly(3,4-ethylenedioxythiophene) (PEDOT) fiber was chemically synthesized by the polymerization of 2,5-dihalo-3,4-ethylenedioxythiophene in the presence of BF₃ without a template. The resulting conductive PEDOT fiber exhibited conductivity in the range of 150–250 S/cm (pressed powder pellet). The thermal stability of PEDOT was also improved and UV-spectroscopy analysis of a film exhibited a strong absorption band at 460 nm. The well-defined needle-shaped fibers of PEDOT were examined by SEM, and the average length and diameter of the fibers were 10 and 0.4 μm, respectively.     

Melt blending of carbon nanotubes/polyaniline/polypropylene compounds and their melt spinning to conductive fibres

Blends of polypropylene with polyaniline and multi-walled carbon nanotubes have been prepared and melt spun to fibre filaments. The resulted filaments have been characterised regarding conductivity, morphology, thermal and mechanical properties. DSC suggests that carbon nanotubes act as nucleating sites for PP/polyaniline blend. Electrical conductivity has been measured for blends with extruded rod shape, as-spun fibre filaments and fibres made under draw ratio of four. Polypropylene containing 20 wt% polyaniline polymer modified with 7.5 wt% carbon nanotubes shows the maximum conductivity among all the samples, about 0.16 S/cm.     

Composite films of nanostructured polyaniline with poly(vinyl alcohol)

The uniform composite films of nanostructured polyaniline (PANI) (e.g. nanotubes or nanorods with 60–80 nm in diameter) were successfully fabricated by blending with water-soluble poly(vinyl alcohol) (PVA) as a matrix. The PANI nanostructures were synthesized by a template-free method in the presence of β-naphthalene sulfonic acid (β-NSA) as a dopant. The molecular structures of PANI–β-NSA and the related composite films were characterized by UV–Vis absorption spectrum, FTIR spectrum and X-ray diffraction. It was found that the electrical, thermal and mechanical properties of the composite films were affected by the content of nanostructured PANI–β-NSA in the PVA matrix. The composite film with 16% PANI–β-NSA showed the following physical properties: room-temperature conductivity is in the range 10⁻² S/cm, tensile strength ∼603 kg/cm², tensile modulus ∼4.36×10⁵ kg/cm² and ultimate elongation ∼80%.     

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.     

A three-in-one improvement in thermoelectric properties of polyaniline brought by nanostructures

β-Naphthalene sulfonic acid doped polyaniline nanotubes (PANI NT) was synthesized, a sample without specific nanostructure was prepared as a reference. Seebeck coefficient, electrical and thermal conductivity of both samples were studied. For a PANI NT prepared with an aniline/NSA ratio of 4:1, the Seebeck coefficient had a value of 212.4 μV/K at 300 K, which was 7 times higher than that of the reference sample. Meanwhile, electrical conductivity almost doubled, changed from 0.0045 to 0.0077 S/cm, while the thermal conductivity reduced by 27.5%, dropped from 0.29 to 0.21 W/m K. Finally, thermoelectric performance was evaluated by calculating the thermoelectric power factor and figure of merit, and there was a two orders of magnitude's increase for the tube-like PANI. A series of PANI NTs prepared under different aniline/NSA ratio were also investigated for searching an optimized performance. Tubular nanostructure was proved to be effective for enhancing the thermoelectric performance. This idea might be applicable to other organic thermoelectric materials as well.     

Preparation and characterization of polyaniline micro/nanotubes with dopant acid mordant dark yellow GG

Polyaniline(PANI) micro/nanotubes doped with novel dopant acid mordant dark yellow GG (AMY GG) were prepared by soft template method in the presence of ammonium persulfate (APS) as an oxidant. It was found that the molar ratio of HCl to aniline and washing method of the products played key roles in the formation of PANI micro/nanotubes. Changing the molar ratio of HCl to aniline, the typical morphology of PANI could be changed from nanotubes to microtubes. In order to get the final product, different solvents were tried to wash away the by-products. After the by-products were removed by water/methonal/ether, the PANI micro/nanotubes appeared. The morphology of PANI micro/nanotubes was confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The chemical structure and thermal stability of PANI micro/nanotubes were examined by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) and the thermogravimetric analysis (TGA). The formation mechanism of PANI micro/nanotubes was also discussed.